Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith

ABSTRACT

Hindered amines substituted on the N-atom with an —O—E—OH moiety are particularly effective in stabilizing polyolefin and automotive coating compositions against the deleterious effects of oxidative, thermal and actinic radiation where the presence of the OH group on the compounds adds important properties not attainable by the use of normal —O—E moieties.

[0001] The instant invention pertains to hindered amine compounds whichare substituted on the N-atom by N-alkoxy moieties containing one tothree hydroxyl groups. These materials are particularly effective instabilizing polyolefins, especially thermoplastic polyolefins, againstthe deleterious effects of oxidative, thermal and actinic radiation. Thecompounds are also effective in stabilizing acid catalyzed and ambientcured coatings systems.

BACKGROUND OF THE INVENTION

[0002] 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and4-oxo-1-oxyl-2,2,6,6-tetramethylpiperidine are reported to have beenused to trap carbon centered radicals formed from methano ethanol,isopropanol and sec butanol by S. Nigam et al. J. Chem. Soc., Trans.Faraday Soc. 1, 1976, 72, 2324 and by K. -D. Asmus et al., Int. J.Radiat. Biol., 1976, 29, 211.

[0003] U.S. Pat. No. 5,627,248 and European Patent ApplicationNo.135,280 A2 describe, respectively, difunctional and monofunctionalliving free radical polymerization initiators, some of which containhindered amine ethers substituted by hydroxy groups. These compoundsdiffer substantially in structure and performance from the instantcompounds.

[0004] European Patent Application No. 427,672 A1 and U.S. Pat. No.4,972,009 mention, but do not exemplify, respectively, hydroxylamine andnitrone structures, some of which contain C₁-C₄ hydroxyalkoxysubstituted 2,2,6,6-tetramethylpiperidine derivatives. Such structuresare outside the scope of the instant invention.

[0005] U.S. Pat. No. 5,204,473 describes N-hydrocarbyloxy hindered aminederivatives that are prepared exclusively from organic compoundscontaining only carbon and hydrogen atoms. Such compounds arestructurally quite different from the instant compounds.

[0006] U.S. Pat. No. 5,004,770 describes hindered amine compounds whichare substituted on the N-atom by alkoxy moieties which alkoxy groups arethemselves unsubstituted. These compounds are especially useful inpolymers including polybutadiene, polystyrene, ABS, polyacetal,polyamide, polyester, polyurethane and polycarbonate.

[0007] U.S. Pat. No. 5,096,950 also describes hindered amine compoundswhich are substituted on the N-atom by alkoxy moieties which alkoxygroups are themselves unsubstituted. These compounds are found to beuseful in polyolefins.

[0008] The instant compounds are N-alkoxy substituted derivatives of2,2,6,6tetraalkylpiperidines where the alkoxy group is substituted byone to three hydroxy moieties. The instant compounds also compriseN-alkoxy bridged derivatives of the 2,2,6,6tetraalkylpiperidines wherethe alkoxy moiety, which is substituted by one to three hydroxy groups,is shared by two hindered amine molecules. The free hydroxy moieties ofthese compounds may be reacted with carboxylic acids, acid chlorides oresters to form simple esters or polyesters, or with isocyanates to formurethanes or polyurethanes.

[0009] The instant compounds, because of their low bascity which isshared by the simple unsubstituted N-alkoxy compounds cited in the twopatents mentioned above, are of particular value in the stabilization ofpolyolefins and automotive coating compositions where the activity ofthe more basic hindered amine stabilizes is significantly reducedbecause of interaction with the polymer substrate or acid catalyticsystem needed for curing such substrate.

[0010] Examples of polyolefin compositions in which the instantcompounds are effective include flame retardant polyolefins where acidicresidues from the decomposition of the halogenated flame retardantsdeactivate hindered amines not having the N—OR group, greenhouse filmsand agricultural mulch films where acidic residues from pesticidesinterfere with the activity of “normal” hindered amine stabilizers, andin thermoplastic polyolefins where pigment interactions with basichindered amine stabilizers interfere with painting the substratesurfaces. Examples of coating compositions in which the instantcompounds are effective include melamine crosslinked thermoset acrylicresins, which are cured using strong acids that interact with basichindered amine stabilizers. The instant compounds are also effective inacrylic alkyd or polyester resins with isocyanate crosslinking agents,and in epoxy resins with carboxylic acid, anhydride, or aminecrosslinking agents.

[0011] While the unsubstituted N—OR compounds described in U.S. Pat.Nos. 5,004,770 and 5,096,950 also perform well in the compositionsdescribed in the paragraph above, the instant compounds differsignificantly in both structure and in performance from the prior artcompounds by virtue of the presence of the one to three free hydroxygroups present on the N-alkoxy moiety. These hydroxyl groups in theinstant compounds provide said compounds with superior antistaticproperties, compatibility in more polar environments such aspolyurethane based and in water-borne automotive coating systems, and instabilizing painted automotive thermoplastic olefin structures.

[0012] The instant compounds are particularly suited for

[0013] (a) providing superior compatibility in polycarbonates andpolycarbonate/ABS blends compared to the N—OE prior art compounds; and

[0014] (b) providing superior compatibility in polyesters and polyamidescompared to the prior art N—OE compounds.

OBJECTS OF THE INVENTION

[0015] There are two objects to the instant invention which are:

[0016] 1. Novel compounds having on the 1-position of the hindered aminea moiety —SE—OH where the OH group provides important properties; and

[0017] 2. Compositions stabilized by the novel compounds describedabove.

DETAILED DISCLOSURE

[0018] The instant invention pertains to novel compounds having 1-alkoxysubstituted hindered amine derivatives where the alkoxy moiety issubstituted by one to three hydroxy groups as described in formulas (1)to (15); or to novel compounds having 1-alkoxy bridged hindered aminederivatives where the alkoxy moiety, substituted by one to three hydroxygroups, is shared by two hindered amine molecules as described informulas (16) to (28); or to oligomeric or polymeric hindered aminemolecules made from the reaction of dialkyl esters or isocyanates withhydroxy substituted N-alkoxy derivatves of4-hydroxy-2,2,6,6-tetraalkylpiperidine as described in formula (29); orto simple diester or urethane derivatives of hydroxy substitutedN-alkoxy derivatives of 4-hydroxy-2,2,6,6-tetramethylpiperidine asdescribed in formula (30)

[0019] G₁ and G₂ are independently alkyl of 1 to 4 carbon atoms, or G₁and G₂ together are pentamethylene; preferably G₁ and G₂ are eachmethyl;

[0020] E is a straight or branched chain alkylene of 1 to 18 carbonatoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18carbon atoms, a straight or branched chain alkylene of 1 to 4 carbonatoms substituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;

[0021] b is 1, 2 or 3 with the proviso that b cannot exceed the numberof carbon atoms in E or L, and when b is 2 or 3, each hydroxyl group isattached to a different carbon atom of E or L; the two hindered aminegroups are generally, but not always, attached to two different carbonatoms of L;

[0022] in each of the formulas (1) to (15)

[0023] m is 0 or 1;

[0024] R₁ is hydrogen, hydroxyl or hydroxymethyl;

[0025] R₂ is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to12 carbon atoms;

[0026] n is 1 to 4;

[0027] when n is 1,

[0028] R₃ is alkyl of 1 to 18 carbon atoms,alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkylis interrupted by oxygen, an acyl radical of an aliphatic or unsaturatedaliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms,an acyl radical of a cycloaliphatic carboxylic or carbamic acidcontaining 7 to 12 carbon atoms, or acyl radical of an aromatic acidcontaining 7 to 15 carbon atoms;

[0029] when n is 2,

[0030] R₃ is alkylene of 2 to 18 carbon atoms, a divalent acyl radicalof an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic acidcontaining 8 to 15 carbon atoms;

[0031] when n is 3,

[0032] R₃ is a trivalent acyl radical of an aliphatic or unsaturatedaliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or atrivalent acyl radical of an aromatic tricarboxylic acid containing 9 to15 carbon atoms;

[0033] when n is 4,

[0034] R₃ is a tetravalent acyl radical of an aliphatic or unsaturatedaliphatic tetracarboxylic acid, especially 1,2,3,4-butanetetracarboxylicacid, 1,2,3,4-but-2-enetetracarboxylic acid,1,2,3,5-pentanetetracarboxylic acid and 1,2,4,5-pentanetetracarboxylicacid, or R₃ is a tetravalent acyl radical of an aromatic tetracarboxylicacid containing 10 to 18 carbon atoms;

[0035] p is 1 to 3,

[0036] R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6carbon atoms;

[0037] when p is 1,

[0038] R₅ is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical ofan aliphatic or unsaturated aliphatic carboxylic or carbamic acidcontaining 2 to 18 carbon atoms, an acyl radical of a cydoaliphaticcarboxylic or carbamic acid containing 7 to 12 carbon atoms, an acylradical of an aromatic carboxylic acid containing 7 to 15 carbon atoms,or R₄ and R₅ together are —(CH₂)₅CO—, phthaloyl or a divalent acylradical of maleic acid;

[0039] when p is 2,

[0040] R₅ is alkylene of 2 to 12 carbon atoms, a divalent acyl radicalof an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic acidcontaining 8 to 15 carbon atoms;

[0041] when p is 3,

[0042] R₅ is a trivalent acyl radical of an aliphatic or unsaturatedaliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or atrivalent acyl radical of an aromatic tricarboxylic acid containing 9 to15 carbon atoms;

[0043] when n is 1,

[0044] R₆ is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18carbon atoms, —NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of 2 to 36carbon atoms,

[0045] when n is 2,

[0046] R₆ is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2to 18 carbon atoms, —NH-alkylene-NH— of 2 to 18 carbon atoms or—N(alkyl)-alkylene-N(alkyl)— of 2 to 18 carbon atoms, or R₆ is4methy-1,3-phenylenediamino,

[0047] when n is 3,

[0048] R₆ is a trivalent alkoxy radical of a saturated or unsaturatedaliphatic triol containing 3 to 18 carbon atoms,

[0049] when n is 4,

[0050] R₆ is a tetravalent alkoxy radical of a saturated or unsaturatedaliphatic tetraol containing 4 to 18 carbon atoms,

[0051] R₇ and R₈ are independency chlorine, alkoxy of 1 to 18 carbonatoms, —O—T₁, amino substituted by 2-hydroxyethyl, —NH(alkyl) of 1 to 18carbon atoms, —N(alkyl)T₁ with alkyl of 1 to 18 carbon atoms, or—N(alkyl)₂ of 2 to 36 carbon atoms,

[0052] R₉ is a divalent oxygen atom, or R₉ is a divalent nitrogen atomsubstituted by either hydrogen, alkyl of 1 to 12 carbon atoms or T₁

[0053] R₁₀ is hydrogen or methyl,

[0054] q is 2 to 8,

[0055] R₁₁ and R₁₂ are independently hydrogen or the group T₂

[0056] R₁₃ is hydrogen, phenyl, straight or branched alkyl of 1 to 12carbon atoms, alkoxy of 1 to 12 carbon atoms, straight or branched alkylof 1 to 4 carbon atoms substituted by phenyl, cycloalkyl of 5 to 8carbon atoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of 2 to 12carbon atoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1to 4 carbon atoms, or silyl or silyloxy substituted three timesindependently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms orby alkoxy of 1 to 4 carbon atoms;

[0057] R₁₄ is hydrogen or silyl substituted three times independently byhydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of 1to 4 carbon atoms;

[0058] d is or 1;

[0059] h is 0 to 4;

[0060] k is 0 to 5;

[0061] x is 3 to 6;

[0062] y is 1 to 10;

[0063] z is an integer such that the compound has a molecular weight of1000 to 4000 amu,

[0064] R₁₅ is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to8 carbon atoms, especially branched alkylamino of 3 to 8 carbon atomssuch as tert-octylamino, —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms,or —N(alkyl)₂ of 2 to 16 carbon atoms,

[0065] R₁₆ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoylsubstituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substitutedonce by chlorine and once by R₁₅, or s-triazinyl substituted twice byR₁₅ with the condition that the two R₁₅substituents may be different;

[0066] R₁₇ is chlorine, amino substituted by alkyl of 1 to 8 carbonatoms or by T₁, —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms,—N(alkyl)₂ of 2 to 16 carbon atoms, or the group T₃

[0067] R₁₈ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoylsubstituted by alkyl of 1 to 4 carbon atoms, s-triazinyl substitutedtwice by —N(alkyl)₂ of 2 to 16 carbon atoms or s-triazinyl substitutedtwice by —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms;

[0068] L is straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbonatoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chainalkylene of 1 to 4 carbon atoms substituted by phenyl or by phenylsubstituted by one or two alkyl of 1 to 4 carbon atoms,

[0069] in formulas (16) to (28), R₁, R₂, R₇, R₈, R₉, R₁₀, R₁₃, R₁₄, d,h,k, m, q, and T₁ have the same meanings as in formulas (1) to (15);

[0070] R₁₉ is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkylis interrupted by oxygen, an acyl radical of an aliphatic or unsaturatedaliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms,an acyl radical of a cycloaliphatic carboxylic or carbamic acidcontaining 7 to 12 carbon atoms, or acyl radical of an aromatic acidcontaining 7 to 15 carbon atoms;

[0071] R₂₀ is alkylene of 2 to 18 carbon atoms, a divalent acyl radicalof an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic acidcontaining 8 to 15 carbon atoms;

[0072] R₂₁ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6carbon atoms;

[0073] R₂₂ is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radicalof an aliphatic or unsaturated aliphatic carboxylic or carbamic acidcontaining 2 to 18 carbon atoms, an acyl radical of a cycloaliphaticcarboxylic or carbamic acid containing 7 to 12 carbon atoms, an acylradical of an aromatic carboxylic acid containing 7 to 15 carbon atoms,or R₄ and R₅ together are —(CH₂)₅CO—, phthaloyl or a divalent acylradical of maleic acid;

[0074] R₂₃ is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of 2 to 6carbon atoms;

[0075] R₂₄ is alkylene of 2 to 18 carbon atoms, a divalent acyl radicalof an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acidcontaining 2 to 18 carbon atoms, a divalent acyl radical of acycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12 carbonatoms, or a divalent acyl radical of an aromatic dicarboxylic addcontaining 8 to 15 carbon atoms;

[0076] R₂₅ is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18carbon atoms, —NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of 2 to 36carbon atoms,

[0077] R₂₆ is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of2 to 18 carbon atoms, —NH-alkylene-NH— of 2 to 18 carbon atoms or—N(alkyl)-alkylene-N(alkyl)— of 3 to 18 carbon atoms,

[0078] in formulas (29) and (30), G is a carbon centered diradicalderived from a primary, secondary or tertiary alcohol G—OH, where

[0079] z is as defined above, and

[0080] G is straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 8 carbon atoms, cydoalkenylene of 5 to 8 carbonatoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chainalkylene of 1 to 4 carbon atoms substituted by phenyl or by phenylsubstituted by one or two alkyl of 1 to 4 carbon atoms, with the provisothat in formula (29) successive hindered amine moieties can be orientedin either a head to head or head to tail fashion;

[0081] T₄ is hydrogen or

[0082] R₂₇ is a straight or branched chain alkylene of 1 to 18 carbonatoms, cydoalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenyleneor —NH-alkylene-NH— of 2 to 18 carbon atoms including5amino-1-aminomethyl-1,3,3-trimethylcyclohexane and —NH-xylylene-NH—;

[0083] R₂₈ is alkyl of 1 to 4 carbon atoms;

[0084] R₂₉ is a straight or branched chain alkyl or —NH-alkyl of 1 to 18carbon atoms or —NH-cycloalkyl of 5 to 8 carbon atoms; and

[0085] with the further proviso that in formulas (1) and (2), when b is1, E is not methyl, ethyl, 2-propyl or 2-methyl-2-propyl.

[0086] Preferably, G₁ and G₂ are each methyl.

[0087] Preferably, in formulas (1) to (28), b is 1 or 2, most preferably1.

[0088] When b is 1, E—OH and L—OH are respectively a carbon-centeredradical or diradical formed preferably from 2-methyl-2-propanol,2-propanol, 2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol,1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol,1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol,cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or1-phenyl-1-ethanol; most preferably E—OH and L—OH are formed from2-methyl-2-propanol or cyclohexanol.

[0089] When b is 2, E—OH and L—OH are respectively a carbon-centeredradical or diradical formed preferably from 1,2-ethanediol,1,2-propanedial, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol,1,3-cyclohexanediol or 1,4-cyclohexanediol; most preferably E—OH andL—OH are formed from 1,4-butanediol, 2,2-dimethyl-1,3-propanediol,1,2-cyclohexanediol, 1,3-cydohexanediol or 1,4-cyclohexanediol.

[0090] When b is 3, E—OH and L—OH are respectively a carbon-centeredradical or diradical formed from glycerol,1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol; most preferably E—OH and L—OH are formed fromglycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol.

[0091] Preferably in formulas (29) and (30), —G—O—is formed fromethanol, phenethyl alcohol, cyclohexanol or 2-methyl-2-propanol(=tert-butyl alcohol).

[0092] Preferably in formula (3), m is 0, R₁ is hydrogen orhydroxymethyl, and R₂ is hydrogen; or m is 1, R₁ is hydroxy orhydroxymethyl, and R₂ is hydrogen, methyl or ethyl.

[0093] Preferably in formula (5), R₂ is hydrogen or dodecyl.

[0094] Preferably in formula (6), n is 1 or 2, and when n is 1, R₃ isallyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl,tetradecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl,methoxycarbonylpentanoyl or methoxycarbonyinonanoyl; or when n is 2, R₃is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl or cis-or trans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3-trimethylcyclohexane.

[0095] Preferably in formula (7), p is 1 or 2, and when p is 1, R4 ishydrogen and R₅ is butyl; or R₄ and R₅ together are the divalent acylradical of maleic acid; or when p is 2, R₄ is hydrogen or acetyl, and R₆is 1,6-hexanediyl.

[0096] Preferably in formula (8), n is 1 or 2, and when n is 1, R₆ isethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; orwhen n is 2, R₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino,hexamethylenediamino, or 4-methyl-1,3-phenylenediamino.

[0097] Preferably in formula (9), R₇ and R₈ are independently chlorine,octylamino, tert-octyl-amino or amino substituted by T₁ and ethyl, butylor dodecyl; and R₉ is a divalent nitrogen atom substituted by ethyl,butyl or dodecyl.

[0098] Preferably in formula (10), q is 2, 4 or 6, R₇ is chlorine,octylamino, octadecylamino or amino substituted by T₁ and ethyl, butylor dodecyl; and R₁₀ is hydrogen.

[0099] Preferably in formula (11), n is 3, p is 2, R₂ is ethyl, butyl ordodecyl; and one of R₁₁ or R₁₂ is T₂, and the other is hydrogen.

[0100] Preferably in formula (12), k is 3, R₉ is a divalent oxygen atomor is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl,R₁₃ is hydrogen or methyl, and when d is 0, x is 5 or 6, and when d is1, x is 3 or 4.

[0101] Preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or 3, yis 1-8, R₉ is a divalent oxygen atom or a divalent nitrogen atomsubstituted by ethyl, butyl or dodecyl, R₁₃ is hydrogen, methyl, ethyl,methoxy or ethoxy, and R₁₄ is hydrogen or trimethylsilyl.

[0102] Preferably in formula (14), R₉ is a divalent oxygen atom, R₁₀ ishydrogen or methyl, m is 0 and z is an integer such that the molecularweight of the compound is 1500-3000 amu.

[0103] Preferably in formula (15) q is 6, y is 1-7, R₁₅ istert-octylamino, morpholino, amino substituted by T₁ and butyl, whichmay also be designated as T₁-butylamino, R₁₆ is hydrogen, acetyl,ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl,2,4-bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice byT₁-butylamino or s-triazinyl substituted once by diethylamino ordibutylamino and once by T₁-butylamino, R₁₇ is dibutylamino,diethylamino, T₁-butylamino or R₁₇ is T₃ where R₁₈ is acetyl orethylcarbamoyl.

[0104] Preferably in formula (17), m is 0, R₁ is hydrogen orhydroxymethyl, and R₂ is hydrogen; or m is 1, R₁ is hydroxy orhydroxymethyl, and R₂ is hydrogen or methyl.

[0105] Preferably in formula (19), R₂ is hydrogen or dodecyl. Preferablyin formula (20), R₁₉ is hydrogen, allyl, acryloyl, methacryloyl,octadecanoyl or hexadecanoyl.

[0106] Preferably in formula (21), R₂₀ is succinyl, glutaryl, adipoyl,sebacoyl, 1,6-hexane-dicarbamoyl, or cis- ortrans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3-trimethylcyclohexane.

[0107] Preferably in formula (22), R₂₁ is hydrogen and R₂₂ is hydrogenor butyl; or R₂₁ and R₂₂ together are the divalent acyl radical ofmaleic acid.

[0108] Preferably in formula (23), R₂₃ is hydrogen or acetyl, and R₂₄ isethylene or hexamethylene.

[0109] Preferably in formula (24), R₂₅ is ethoxy, 6-methyl-1-heptyloxy,ethylamino, butylamino or octylamino.

[0110] Preferably in formula (25), R₂₆ is 1,2-ethanedioxy,14-butanedioxy, ethylenediamino or hexamethylenediamino.

[0111] Preferably in formula (26), R₇ and R₈ are independently chlorine,octylamino, tert-octylamino, octadecylamino, T₁-ethylamino,T₁-butylamino or T₁-dodecylamino, and R₉ is a divalent nitrogen atomsubstituted by ethyl, butyl or dodecyl.

[0112] Preferably in formula (27), q is 2, 4 or 6, R₇ is chlorine,octylamino, octadecylamino, T₁-ethylamino, T₁-butylamino orT₁-dodecylamino, and R₁₀ is hydrogen.

[0113] Preferably in formula (28), d is 0 or 1, h is 0-2, k is 0 or 3,R₉ is a divalent oxygen atom or a divalent nitrogen atom substituted byethyl, butyl or dodecyl, R₁₃ is hydrogen, methyl, ethyl, methoxy orethoxy, and R₁₄ is hydrogen or trimethylsilyl.

[0114] Preferably in formula (29), R₂₇ is ethylene, trimethylene,tetramethylene, octamethylene, 1,6-diaminohexane or5-amino-1-aminomethyl-1,3,3-trimethylcydohexane; z is an integer suchthat the molecular weight of the compound is 1500-3000 amu, R₂₈ ismethyl or ethyl, and G is ethylene, 1,2-cyclohexanediyl,1,3-cyclohexanediyl, 1,4-cyclohexanediyl, —CH(C₆H₅)CH₂— or —CH₂C(CH₃)₂—.

[0115] Preferably in formula (30), R₂₉ is pentadecyl, heptadecyl,butylamino or cyclohexylamino.

[0116] Still more preferred embodiments of the instant invention are thecompounds of formulas (1) to (30) where E—OH, L—OH and G—O— are formedfrom 2-methyl-2-propanol (=tert-butyl alcohol) or cyclohexanol.

[0117] Most preferably in formula (6), when n is 1, R₃ is acryloyl,methacrloyl, glycidyl, octadecanoyl, hexadecanoyl,methoxycarbonylpropionyl, methoxycarbonylbutyryl,methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R₃is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl or cis-or trans-5carbamoyl-1-(carbamoylmethyl-1,3,3-trimethylcyclohexane.

[0118] Most preferably in formula (7), p is 1 or 2, and when p is 1, R₄is hydrogen and R₈ is hydrogen or butyl; or when p is 2, R₄ is hydrogen,and R₅ is 1,6-hexanediyl.

[0119] Most preferably in formula (9), R₇ is chlorine, octylamino orT₁-butylamino, R₈ is chlorine or T₁-butylamino, and R₉ is a divalentnitrogen atom substituted by butyl.

[0120] Most preferably in formula (10), q is 6, R₇ is T₁-butylamino; andR₁₀ is hydrogen.

[0121] Most preferably in formula (11), n is 3, p is 2, and one of R₁₁,or R₁₂ is T₂, and the other is hydrogen.

[0122] Most preferably in formula (12), k is 3, R₁₃ is a divalent oxygenatom, R₁₃ is hydrogen or methyl, andd is 0, x is 5 or 6, and when d is1, x is 3 or 4.

[0123] Most preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or3, y is 1-8, R₉ is a divalent oxygen atom, R₁₃ is hydrogen, methyl,ethyl, methoxy or ethoxy, and R₁₄ is hydrogen or trimethylsilyl.

[0124] Most preferably in formula (15) q is 6, y is 1-7, R₁₅ isT₁-butylamino, R₁₆ is hydrogen, acetyl, ethylcarbamoyl,2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl,s-triazinyl substituted twice by T₁-butylamino or s-triazinylsubstituted once by diethylamino or dibutylamino and once byT₁-butylamino, R₁₇ is dibutylamino, diethylamino, T₁-butylamino or R₁₇is T₃ where R₁₈ is acetyl or ethylcarbamoyl.

[0125] Most preferably in formula (20), R₁₉ is hydrogen, octadecanoyl orhexadecanoyl.

[0126] Most preferably in formula (22), R₂₁ is hydrogen and R₂₂ ishydrogen or butyl.

[0127] Most preferably in formula (23), R₂₃ is hydrogen, and R₂₄ ishexamethylene.

[0128] Most preferably in formula (26), R₇ is chlorine, octylamino orT₁-butylamino, R₉ is chlorine or T₁-butylamino, and R₉ is a divaletnirogen atom substituted by butyl.

[0129] Most preferably in formula (27), q is 6, R₇ is T₁-butylamino, andR₉ is a divalent nitrogen atom substituted by butyl.

[0130] Most preferably in formula (29), R₂₇ is ethylene, trimethylene,tetramethylene or octamethylene, z is an integer sucn that the molecularweight of the compound is 1500 to 2000 amu, and R₂₈ is methyl.

[0131] Most preferably in formula (30), R₂₉ is pentadecyl or heptadecyl.

[0132] Still more preferred embodiments of the instant invention are thecompounds of formulas (1) to (30) where E—OH, L—OH and —G—O— are formedfrom 2-methyl-2-propanol (=tert-butyl alcohol).

[0133] Especially preferred compounds of formula (6) are those where nis 1, R₃ is acryloyl, methacryloyl, glycidyl, octadecanoyl,hexadecanoyl, methoxycarbonylpropionyl or methoxycarbonylbutyryl, andwhere n is 2, R₃ is succinyl, glutaryl, adipoyl or sebacoyl.

[0134] Especially preferred compounds of formula (7) are those where R₄is hydrogen, and when p is 1, R₅ is hydrogen or butyl, or when p is 2,R₅ is hexamethylene.

[0135] Especially preferred compounds of formula (9) are those where R₇is chlorine, octylamino or T₁-butylamino, R₈ is T₁-butylamino, and R₉ isa divalent nitrogen atom substituted by butyl.

[0136] Especially preferred compounds of formula (10) are those where qis 6, R₇ is T₁-butylamino and R₁₀ is hydrogen.

[0137] Especially preferred compounds of formula (11) are those where nis 3, p is 2, one of R₁₁ or R₁₂ is T₂ and the other is hydrogen.

[0138] Especially preferred compounds of formula (12) are those where dis 1, k is 3, x is 3 or 4, R₉ is divalent oxygen atom, and R₁₃ ismethyl.

[0139] Especially preferred compounds of formula (13) are those where kis 3, y is 4-8. R₉ is a divalent oxygen atom, R₁₃ is hydrogen or methyl,d and h are 0, R₁₄ is hydrogen, or d is 1 and h is 0, and R₁₄ istrimethylsilyl.

[0140] Especially preferred compounds of formula (14) are those where mis 0, R₉ is a divalent oxygen atom, R₁₀ is hydrogen or methyl, and z isan integer such that the molecular weight of the compound is 1500-3000amu.

[0141] Especially preferred compounds of formula (15) are those where qis 6, y is 1-7, R₁s is T₁-butylamino, R₁₆ is hydrogen, acetyl,ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl,2,4-bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice byT₁-butylamino or s-triazinyl substituted once by diethylamino ordibutylamino and once by T₁-butylamino, R₁₇ is dibutylamino,diethylamino, or T₃ where R₁₈ is acetyl or ethylcarbamoyl.

[0142] Especially preferred compounds of formula (20) are those whereR₁₉ is hydrogen, octadecanoyl or hexadecanoyl.

[0143] Especially preferred compounds of formula (21) are those whereR₂₀ is succinyl, glutaryl, adipoyl or sebacoyl.

[0144] Especially preferred compound of formula (30) is that where R₂₉is heptadecyl.

[0145] The instant invention also pertains to a polymer compositioncontaining an effective stabilizing amount of one or more compoundsselected from the compounds of formula (1) to formula (30) as describedabove.

[0146] Preferably, the organic material is a natural, semi-synthetic orsynthetic polymer, especially a thermoplastic polymer.

[0147] Most preferably, the polymer is a polyolefin, especially athermoplastic polyolefin useful in automotive coatings and applicationsor a urethane based automotive coating.

[0148] The compounds of this invention exhibit superior hydrolyticstability, handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

[0149] In general polymers which can be stabilized include

[0150] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbomene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),branched low density polyethylene (BLDPE).

[0151] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0152] a) radical polymerisation (normally under high pressure and atelevated temperature).

[0153] b) catalytic polymerisation using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(II) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerisation medium. The catalysts can be used by themselves inthe polymerisabon or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, Iha and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0154] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0155] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethyleneloctene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbomene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic addcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0156] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0157] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0158] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0159] 7. Graft copolymers of styrene or α-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylnitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

[0160] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated or sulfochlonnated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl fluoride, polyvinylidene fluoride, aswell as copolymers thereof such as vinyl chloride/vinylidene chloride,vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetatecopolymers.

[0161] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0162] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/ butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

[0163] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0164] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0165] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0166] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0167] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0168] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4,-rimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0169] 17. Polyureas, polyimides, polyamide-imides andpolybenzimidazoles.

[0170] 18. Polyesters derived from dicarboxlic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

[0171] 19. Polycarbonates and polyester carbonates.

[0172] 20. Polysulfones, polyether sulfones and polyether ketones.

[0173] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenoy/formaldehyde resins, urea/formnaldehyde resins andmelamine/formaldehyde resins.

[0174] 22. Drying and non-drying alkyd resins.

[0175] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0176] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0177] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, polyisocyanates or epoxyresins.

[0178] 26. Crosslinked epoxy resins derived from polyepoxides, forexample from bisglycidyl ethers or from cycloaliphatic diepoxides.

[0179] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0180] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6andcopolymers, PA/HDPE, PA/PP, PA/PPO.

[0181] 29. Naturally occurring and synthetic organic materials which arepure monomeric compounds or mixtures of such compounds, for examplemineral oils, animal and vegetable fats, oil and waxes, or oils, fatsand waxes based on synthetic esters (e.g. phthalates, adipates,phosphates or trimellitates) and also mixtures of synthetic esters withmineral oils in any weight ratios, typically those used as spinningcompositions, as well as aqueous emulsions of such materials.

[0182] 30. Aqueous emulsions of natural or synthetic rubber, e.g.natural latex or latices of carboxylated styrene/butadiene copolymers.

[0183] 31. Polysiloxanes such as the soft, hydrophilic polysiloxanesdescribed, for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

[0184] 32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

[0185] 33. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer.

[0186] 34. Epoxymelamine resins such as light-stable epoxy resinscrosslinked by an epoxy functional coetherified high solids melamineresin such as LSE-4103 (Monsanto).

[0187] In general, the compounds of the present invention are employedin from about 0.01 to about 5% by weight of the stabilized composition,although this will vary with the particular substrate and application.An advantageous range is from about 0.05 to about 3%, and especially0.05 to about 1%.

[0188] The stabilizers of the instant invention may readily beincorporated into the organic polymers by conventional techniques, atany convenient stage prior to the manufacture of shaped articlestherefrom. For example, the stabilizer may be mixed with the polymer indry powder form, or a suspensionor emulsion of the stabilizer may bemixed with a solution, suspension, or emulsion of the polymer. Theresulting stabilized polymer compositions of the invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

[0189] 1. Antioxidants

[0190] 1.1. Alkylated Monophenols, for Example

[0191] 2,6di-tert-butyl-4-methylphenol

[0192] 2-tert-butyl-4,6-dimethylphenol

[0193] 2,6-di-tert-butyl-4-ethylphenol

[0194] 2,6-di-tert-butyl-4-n-butylphenol

[0195] 2,6di-tert-butyl-4-i-butylphenol

[0196] 2,6di-cyclopentyl4-methylphenol

[0197] 2-(α-methylcyclohexyl)-4,6-dimethylphenol

[0198] 2,6-di-octadecyl-4-methylphenol

[0199] 2,4,6-tri-cyclohexylphenol

[0200] 2,6di-tert-butyl-4-methoxymethylphenol

[0201] 1.2. Alkylated Hydroguinones, for Example

[0202] 2,6di-tert-butyl-4-methoxyphenol

[0203] 2,5-di-tert-butyl-hydroquinone

[0204] 2,5di-tert-amyl-hydroquinone

[0205] 2,6-diphenyl-4-octadecyloxyphenol

[0206] 1.3. Hydroxylated Thiodiphenyl Ethers, for Example

[0207] 2,2′-bis-(6-tert-butyl-4-methylphenol)

[0208] 2,2′-thio-bis-(4-octylphenol)

[0209] 4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

[0210] 4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

[0211] 1.4. Alkylidene-bisphenols, for Example

[0212] 2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

[0213] 2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

[0214] 2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-pheno]

[0215] 2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

[0216] 2,2′-methylene-bis-(6-nonyl-4-methylphenol)

[0217] 2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

[0218] 2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

[0219] 2,2′-methylene-bis-(4,6-di-tert-butylphenol)

[0220] 2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

[0221] 2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

[0222] 4,4′-methylene-bis-(2,6-di-tert-butylphenol)

[0223] 4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

[0224] 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0225] 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

[0226] 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0227]1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutaneethyleneglycol bis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

[0228] di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

[0229]di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)tert-butylmethylphenyl]terephthalate.

[0230] 1.5. Benzyl Compounds, for Example,

[0231]1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

[0232] di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

[0233] 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acefic acid isooctylester

[0234] bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate

[0235] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

[0236] 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

[0237] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecylester

[0238] 3,5di-tert-butyl4hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

[0239] 1.6. Acylaminophenols, for Example,

[0240] 4hydroxy-lauric acid anilide

[0241] 4hydroxy-stearic acid anilide

[0242]2,4-bis-octylmercapto-6-(3,5tert-butyl-4-hydroxyanilino)-s-triazine

[0243] octyl-N-(3,5di-tert-butyl-4-hydroxyphenyl)-carbamate

[0244] 1.7. Esters of β-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionicacid with monohydric or polyhydric alcohols, for example, methanoldiethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine trisopropanolamine

[0245] 1.8. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)-progionic acid with monohydricor polyhydric alcohols, for example, methanol diethylene glycoloctadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentylglycol tris-hydroxyethyl isocyanurate thiodiethylene glycoldi-hydroxyethyl oxalic acid diamide triethanolamine triisopropanolamine

[0246] 1.9. Amides of β-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionicacid for example,

[0247]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

[0248]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

[0249] N,N′-di-(3,6di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

[0250] 1.10 Diarylamines, for Example,

[0251] diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine, 4,4′di-tert-octyl-diphenylamine,reaction product of N-phenylbenzylamine and 2,4,4-trimethylpentene,reaction product of diphenylamine and 2,4,4-trimethylpentene, reactionproduct of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

[0252] 2. UV Absorbers and Light Stabilizers

[0253] 2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-,5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,4′-octoxy, 3′,5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyethyl)-,3′-dodecyl-5′-methyl-, 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,dodecylated-5′-methyl derivatives; and2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

[0254] 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0255] 2.3. Esters of optionally substituted benzoic acids for example,phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5di-tert-butylhydroxybenzoic addhexadecyl ester.

[0256] 2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acidethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or buffester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

[0257] 2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxymethyl-phenyl undecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

[0258] 2.6. Sterically hindered amines. for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5di-tertbutyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidinyl) sebacate.2-(2-hydroxyethylamino)-4,6-bis{N-[1-(cyclohexyloxy)-2,2,6,6tetramethylpiperidin-4-yl]-butylamino-s-tnazine,oligomer ofN-{[2-(N-2,2,6,6tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl-amino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N″′-tetrakis{2,4-bis[N-(1,2,2,6,6pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;N,N′,N″-tris{2,4-bis[N-(1-cydohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)butylamino]-s-trazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N″′-tetrakis{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.

[0259] 2.7. -Oxalic acid diamides for example,4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

[0260] 2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)}-pheny]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

[0261] 3. Metal deactivators, for example, N,N′-diphenyloxalic aciddiamide, N-salicylal-N′-salicyloylhydrazine,N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

[0262] 4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4di-tert-butylphenyl)phosphite, di-iso-decylpentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylmethylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

[0263] 5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-β-dodecylmercapto)-propionate.

[0264] 6. Hydroxvlamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxyl-amine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0265] 7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecyinitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

[0266] 8. Polvamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0267] 9. Basic co-stabilizers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and Kpalmitate, antimony pyrocatecholate or zinc pyrdcatecholate.

[0268] 10. Nucleating agents, for example, 4-tert-butyl-benzoic acid,adipic acid, diphenylacetic acid.

[0269] 11. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and hydroxides, carbon black, graphite.

[0270] 12. Other additives, for example, plasticizers, lubricants,emulsifiers, pigments, optical brighteners, flameproofing agents,anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearyl thiodipropionate.

[0271] 13. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No.5,175,312,or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0272] The co-stabilizers, with the exception of the benzofuranoneslisted under 11, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

[0273] Further preferred compositions comprise, in addition tocomponents (a) and (b) further additives, in particular phenolicantioxidants, light stabilizers or processing stabilizers.

[0274] Particularly preferred additives are phenolic antioxidants (item1 of the list), sterically hindered amines (item 2.6 of the list),phosphites and phosphonites (item 4 of -the list) andperoxide-destroying compounds (item 5.) of the list.

[0275] Additional additives (stabilizers) which are also particularlypreferred are benzofuran-2-ones, such as described, for example, in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

[0276] The phenolic antioxidant of particular interest is selected fromthe group consisting of n-octadecyl3,5di-tert-butyl4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-ditert-butyl-p-cresol, 2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoaetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

[0277] A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butylhydroxyhydrocinnamate,1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

[0278] The hindered amine compound of particular interest is selectedfrom the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dio ne,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20diaza-21-oxodispiro[5.1.11.2]heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetra-methylpiperidine) and1,2-dibromoethane,

[0279] tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensaton product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine), mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate,

[0280] mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),

[0281] 4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9tetramethyl-1,3,8triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6tetramethylpiperidin-4-yl)succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cydohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cydohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,

[0282]2-(2-hydroxyethylamino)-4,6-bis{N-[1-(cyclohexyloxy)-2,2,6,6tetramethylpiperidin-4-yl]-butylamino-s-triazine,oligomer ofN{[2-(N-2,2,6,6tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl-amino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineand N,N′,N″,N″′-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-ly}-3,3′-ethylenediiminodipropylamine;N,N′,N″-tris{2,4-bis[N-(1-cylohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)butylamino]-s-tdazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpipeddin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′, N″,N″′-tetrakis{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,oligomer ofN{2-[(1-propoxy-2,2,6,6tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, or thecondensation product of 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,6-hexanediamine.

[0283] A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramnethylpipeniine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-(1,2,2,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethylt-4-hydroxypiperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4(1-cyclohexyloxy-2,2,6,6tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)n-butylamino]-s-triazine.

[0284] The instant composition can additionally contain another UVabsorber selected from the group consisting of the s-triazines, theoxanilides, the hydroxybenzophenones, benzoates and theα-cyanoacrylates.

[0285] Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

[0286] Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected fromthe group consisting of

[0287] 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

[0288] 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

[0289]2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

[0290]2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole;and

[0291]2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

[0292] Preferably the 2-hydroxyphenyl-2H-benzotriazole may also beselected from the group consisting of

[0293] (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotrdazole;

[0294] (b)5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

[0295] (c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

[0296] (d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylpheno];

[0297] (e)methylene-2-[4-tert-octyl-6-(2H-benzotriazo]-2-yl)phenol]-2′-[-4-tert-octyl-6-(5-trifluoro-methyl-2H-benzotriazol-2-yl)phenol];

[0298]3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-3-tert-butyl-4-hydroxyhydrocinnamicacid;

[0299] (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;

[0300] (h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;

[0301] (i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

[0302] (j)5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;

[0303] (k)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole,

[0304] (l)5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;

[0305] (m)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzo-triazole;

[0306] (n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

[0307] (o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;

[0308] (p)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzo-triazole;

[0309] (q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzo-triazole;

[0310] (r)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

[0311] (s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0312] (t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

[0313] (u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5(3-hydroxypropyl)phenyl)-2H-benzo-triazole;

[0314] (v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzo-triazole;

[0315] (w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

[0316] (x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0317] (y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0318] (z)5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0319] (aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0320] (bb)5-butylsufonyl-2-(2-hydroxy-3,5-di-tertoctylphenyl)-2H-benzotdazole; and

[0321] (cc)5phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

[0322] Preferably, the other tris-aryl-s-triazine is selected from thegroup consisting of2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

[0323] 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

[0324]2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy(3-do-\tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;and

[0325]2-(2-hydroxyethylamino)4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)amino]-s-triazine.

[0326] The acrylic resin lacquers which can be stabilized against light,moisture and oxygen in accordance to the instant invention areconventional acrylic resin stoving lacquers or thermosetting resinsincluding acrylic/melamine systems which are described, for example, inH. Kittel's “Lehrbuch and Beschichtungen”, Vol. 1, Part 2 on pages 735and 742 (Berlin 1972), “Lackkunstharze” (1977) by H. Wagner and H. F.Sarx on pages 229-238, and in S. Paul's “Surface Coatings. Sciece andTechnology”, (1985).

[0327] The polyester lacquers which can be stabilized against the actionof light and moisture are conventional stoving lacquers described e.g.in H. Wagner and H. F. Sarx, op. cit., on pages 86-99.

[0328] The alkyd resin lacquers which can be stabilized against theaction of light and moisture in accordance with the instant inventionare the conventional stoving lacquers which are used in particular forcoating automobiles (automobile finishing lacquers), for examplelacquers based on alkyd/melamine resins and alkyd/acrylic/melamineresins (see H. Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages99-123). Other crosslinking agents include glycoluril resins, blocked orunblocked isocyanates or epoxy resins. Other lacquers which can bestabilized include those with crosslinkable functionalites such ascarbamate and siloxane.

[0329] The lacquers stabilized in accordance with the invention aresuitable both for metal finish coatings and solid shade finishes,especially in the case of retouching finishes, as well as various coilcoating applications. The lacquers stabilized in accordance with theinvention are preferably applied in the conventional manner by twomethods, either by the single-coat method or by the two-coat method. Inthe latter method, the pigment-containing base coat is applied first andthen a covering coat of clear lacquer over it.

[0330] Although major emphasis in this application is directed toacid-catalyzed baked finishes, it is also to be noted that the compoundsof the present invention are applicable for use in non-acid catalyzedthermoset resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylicand polyester resins, optionally modified with silicon, isocyanates orisocyanurates. The epoxy and epoxy-polyester resins are crosslinked withconventional crosslinkers such as acids, acid anhydrdes, amines and thelike. Correspondingly, the epoxide may be utilized as the crosslinkingagent for various acrylic or polyester resin systems that have beenmodified by the presence of reactive groups on the backbone structure.

[0331] The amount of instant stabilizer compound used is 0.1 to 5% byweight, based on the solvent-free binder, preferably 0.5 to 2% by weightThe binders can be dissolved or dispersed in customary organic solventsor in water or can be solvent-free.

[0332] When used in two-coat finishes, the compounds of the instantinvention can be incorporated in the clear coat or both in the clearcoat and in the pigmented base coat

[0333] To attain maximum light stability, the concurrent use of otherconventional light stabilizers can be advantageous. Examples are UVabsorbers of the benzophenone, benzotriazole, acrylic acid derivatives,oxalanilide, aryl-s-triazine or metal-containing types (e.g. organicnickel compounds). In two-coat systems, these additional lightstabilizers can be added to the clear coat and/or the pigmented basecoat.

[0334] If such combinations of stabilizers are used, the sum of alllight stabilizers is 0.2 to 20% by weight, preferably 0.5 to 5% byweight, based on the film-forming resin.

[0335] When water-soluble, water miscible or water dispersible coatingare desired ammonium salts of acid groups present in the resin areformed. Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

[0336] It is also contemplated that the instant compounds would findparticular value when used with water-soluble inks and related polaroriented utilities where the presence of the OH moiety would provide forbetter compatibility and properties related to such aqueousenvironments.

[0337] The instant compounds are also useful in the stabilization ofacid catalyzed thermoset resins which are disclosed in U.S. Pat. No.5,112,890, the relevant parts of which are incorporated herein byreference.

[0338] These resins are used in baked enamels or stoving lacquers.Hindered amine light stabilizaers are well known to be effective instabilizing a host of organic substrates induding polymers from thedeleterious effects of oxygen and light. Such hindered amine lightstabilizers have been used in the stabilization of hot-crosslinkablealkyd or acrylic metallic stoving lacquers (see U.S. Pat. No. 4,426,472)and in stabilizing add-catalyzed stoving lacquers based onhot-crosslinkable acrylic polyester or alkyl resins (see U.S. Pat. Nos.4,344,876 and 4,426,471). None of the hindered amine light stabilizersof these patents possess structures having an O-substituted hydroxylgroup substituted directly on the N-atom of the hindered amine. Theinstant compounds have such substitution and additionally are even lessbasic than the NOR compounds described in U.S. Pat. No. 5,112,890 as isseen in instant working Example 114.

[0339] In their industrial uses, enamels with high solids content basedon crosslinkable acrylic, polyester, urethane or alkyd resins are curedwith an additional acid catalyst. Light stabilizers containing a basicnitrogen group are generally less than satisfactory in this application.Formation of a salt between the acid catalyst and the light stabilizerleads to incompatibility or insolubility and recipitation of the saltand to a reduced level of cure and to reduced light protective actionand poor resistance to moisture.

[0340] The acid catalyzed thermoset enamels must be stabilized in orderto function acceptably in end-use applications. The stabilizers used arehindered amines, preferably those substituted on the N-atom by an inertblocking group in order to prevent precipitation of the basic amine withthe acid catalyst with a concomitant retardation in cure, optionally incombination with UV absorbers as described above.

[0341] The stabilizers are needed to impart greater retention ofdurability to the cured enamels (as measured by 20° gloss, distinctionof image, cracking or chalking); the stabilizers must not retard cure(normal bake for auto finishes at 121° C.; and low bake repair at 82°C.) as measured by hardness, adhesion, solvent resistance and humidityresistance; the enamel should not yellow on curing and further colorchange on exposure to light should be minimized; the stabilizers shouldbe soluble in the organic solvents normally used in coatingapplications, such as methyl amyl ketone, xylene, n-hexyl acetate,alcohol and the like.

[0342] The instant hindered amine light stabilizers on the N-atom by anO-substituted moiety containing a free hydroxyl group fulfill each ofthese requirements and provide alone or in combination with a UVabsorber outstanding light stabilization protection to the cured acidcatalyzed thermoset enamels.

[0343] The instant invention also pertains to resin systems capable ofbeing fully cured under ambient conditions. For example, applicableresins include alkyd, acrylic, polyester and epoxide resins as describedin S. Paul's “Surface Coatings: Science and Technology” (1985), pages70-310. Various acrylic and modified acrylic resins are described in H.Kittel's “Lehrbuch der Lacke unde Beschichtungen”, Vol. 1, Part 2, onpages 735 and 742 (Berlin 1972), and in “Lackkunstharze” (1977) by H.Wagner and H. F. Sarx, op. cit, on pages 229-238. Typical crosslinkablepolyester resins which can be stabilized against the action of light andmoisture are described e.g. in H. Wagner and H. F. Sarx, op. cit., onpages 86-99. The unmodified and modified alkyd resins which can bestabilized are conventional resins which are used in trade sales,maintenance and automotive refinish coatings. For example, such coatingsare based on alkyd resins, alkyd/acrylic resins and alkyd/silicon reins(see H. Wagner and H. F. Sarx, op. cit., pages 99-123) optionallycrosslinked by isocyanates or epoxy resins.

[0344] In addition various acrylic lacquer coating compositions aredisclosed in U.S. Pat. No. 4,162,249. Other acrylictalkyd resins withpolyisocyanate additives are disclosed in U.S. Pat. No. 4,471,083; andacrylic resins containing either pendant amino ester groups or glycidylgroups are described in U.S. Pat. No. 4,525,521.

[0345] The ambient cured coatings stabilized by the instant compoundsare suitable both for metal finish coatings and solid shade finishes,especially in the casee of retouching finishes. The lacquers stabilizedby the instant compounds are preferably applied in a conventional mannerby two methods, either by the singlecoat method or by the two-coatmethod. In the latter method, the pigment-containing base coat isapplied first and a covering coat of clear lacquer applied over it. Whenused in two-coat finishes, the instant hindered amine compound can beincorporated in the clear coat or both in the clear coat and in thepigmented base coat.

[0346] The instant invention also pertains to abrasion-resistant coatingcompositions suitable for coating over polycarbonates. Such coatings asdescribed in U.S. Pat. No. 5,214,085 comprise a silyl acrylate, aqueouscolloidal silica, a photoinitiator and optionally a polyfunctionalacrylate as well as UV absorbers. Such coatings provide resistance afterprolonged outdoor exposure to sunlight, moisture, thermal cyclingcausing yellowing, delamination and formation of microcracks anddecreasing transparency.

[0347] Related hindered amine stabilizers have been utilizedindividually and in combination with UV absorbers to improve theperformance characteristics of ambient cured coating systems.Notwithstanding such improvements, there still exists a need to furtherretard the photooxidation and photodegradation of such ambient curedsystems and thereby provide increased effectiveness by maintaining thephysical integrity of the coatings. Such effectiveness can be manifestedby prevention of embrittlement, cracking, corrosion, erosion, loss ofgloss, chalking and yellowing of the coating.

[0348] It has now been determined that the aforementioned improvementscanbe achieved by substitution of the N-atom of the hindered amines withan —OR moiety and by the utilization of such derivatives in ambientcured coating systems as is taught in U.S. Pat. No. 5,124,378, therelevant parts of which are incorporated herein by reference. Theinstant compounds are even less basic than the compounds of U.S. Pat.No. 5,124,378 and are particularly well suited for this task. Inparticular, the physical integrity of the coatings is maintained to ahigher degree with significant reduction in loss of gloss and inyellowing. Accordingly, the instant invention relates to the use of theinstant NOR compounds, where the R moiety is further substituted by ahydroxyl group, optionally together with further stabilizers, forstabilizing ambient cured coatings based on alkyd resins; thermosetacrylic resins; acrylic alkyds; acrylic alkyd or polyester resinsoptionally modified with silicon, isocyanates, isocyanurates, ketiminesor oxazolidines; and epoxide resins crosslinked with carboxylic adds,anhydrides, polyamines or mercaptans; and acrylic and polyester resinsystems modified with reactive groups in the backbone thereof andcrosslinked with epoxides; against the degradative effects of light,moisture and oxgen.

[0349] The instant invention also relates to electrodeposited coatingsapplied to metal substrates where various top coats may be appliedthereover. The inclusion of the instant compounds in the E-coat providesdelamination resistance to said E-coats. The primary resins in saidE-coats are acrylic or epoxy resins. These E-coats are described inEuropean patent application EP 0 576 943 A1.

[0350] The instant invention also pertains to UV-cured coating systemsusing unsaturated acrylic resins, polyurethane acrylates, epoxyacrylates, polyester acrylates, unsaturated polyester/styrene resins andsilyl acrylates.

[0351] Synthesis of Compounds

[0352] The instant compounds may be prepared by the reaction oftributyltin hydride and a halogen substituted alcohol to produce carboncentered radicals that are trapped by nitroxyl compounds.

[0353] The instant compounds may also be prepared by coupling an N-oxylhindered amine with a carbon centered radical generated by thephotochemical or thermal decomposition of a perester or dialkyl peroxidein the presence of an alcohol. The bridge compounds described above canbe formed when two nitroxyl radicals couple with the same solventmolecule, especially when the amount of solvent is reduced.

[0354] The preferred method of preparation of the instant compounds isto react an N-oxyl hindered amine with a carbon centered radicalgenerated by mixing an aqueous or alcoholic solution of a metal ion suchas Fe²⁺, Fe³⁺, Cu²⁺ or Cu⁺ and a peroxide such as tert-butylhydroperoxide or hydrogen peroxide in the presence of an alcohol solventat a temperature of 20-80° C. Especially effective is the combination offerrous chloride, ferric chloride or ferrous sulfate, particularlyferrous chloride, or ferric chloride, and hydrogen peroxide. Water maybe added to the alcohol at the beginning of the reaction to improvesolubility of the metal salt or to dissolve an alcohol which is solid atthe reaction temperature. A ligand such as 2,2′-dipyridyl,2,2′6′,2″-terpyridyl, may be added to the reaction mixture. Two nitroxylradicals can sometimes couple with the same solvent molecule to producebridged compoundsdescribed in some formulas listed earlier. Theformation of bridge compounds is more favored when the amount of solventis reduced.

[0355] Some of the instant hydroxy-substituted N-alkoxy compounds may bereacted with monofunctional or difunctional esters, acids or acidchlorides or isocyanates to form polymeric ester or urethanederivatives.

[0356] The following examples are for illustrative purposes only and arenot to be construed to limit the instant invention in any mannerwhatsoever.

EXAMPLE 1 Reaction of 1-Oxyl-2,2,6,6-tetramethyl-piperidin-4-one withCyclohexanol

[0357] A solution of 55 g (0.49 mol) of 30% aqueous hydrogen peroxide isadded dropwise over a 4.25 hour period to a mixture of 23.5 g (0.14 mol)of 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one and 4.0 g (0.020 mol) offerrous chloride tetrahydrate in 14 9 (0.14 mol) of cyclohexanol and 150g of cyclohexane. The reaction temperature is maintained atapproximately 40° C. throughout the addition. The reaction mixture isstirred at 40° C. for three hours after the peroxide addition iscomplete. A second portion of 30% aqueous hydrogen peroxide (10 g, 0.09mol),is added and the reaction mixture is heated at 40° C. for sevenhours. After the mixture is cooled to room temperature, sodium sulfite(5 g) is added. The reaction temperature is carefully brought to 60° C.for one hour to xide. Upon cooling, the organic layer is separated,dried over anhydrous magnesium sulfate, and concentrated to give 22.6 gof a brown oil. The oil is dissolved in cyclohexane and passed throughsilica gel with cyclohexane and then 1:2 (v/v) ethanol/cyclohexane toafford 16.5 g of a yellow oil.

[0358] Analysis by gass chromatography and mass spectrometry shows theproduct to be a mixture which contains at least four isomers of1-(hydroxycyclohexyloxy)-2,2,6,6-tetramethyl-piperidin-4-one.

EXAMPLE 2Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl)]Sebacate

[0359] A solution of 73 g (9.64 mol) of 30% aqueous hydrogen peroxide isadded dropwise over a 3.5 hour period to a mixture of 30.0 g (0.059 mol)of bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-yl) sebacate and 4.7 g(0.024 mol) of ferrous chloride tetrahydrate in 150 a of tert-butylalcohol and 6 g of water. The reaction temperature is kept atapproximately 40° C. throughout the peroxide addition. The reactionmixture is stirred at 40° C. for four hours after the addition iscomplete. The reaction mixture is diluted with 150 g of ethyl acetate. Acolution of 100 g of 20% aqueous sodium sulfite solution is added andthe reaction mixture is stirred for 1.5 hours at 45-60° C. to decomposeexcess peroxide. The aqueous layer is extracted with 100 g of ethylacetate, and the combined organic layers are washed with 200 g of 5%sulfuric acid. Solvent is evaporated to obtain 39.4 g of a pale yellowliquid which is purified by flash chromatography on silica gel with a4:1:5 part mixture (by volume) of ethyl acetate:isopropanol:hexane toafford 19.1 g (49% yield) of the title compound as a pale yellow oil.

[0360]¹Hnmr (CDCl₃): δ=3.65 ppm (4H, —NOCH_(2″))

EXAMPLE 3 Reaction of Bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl)Sebacate with Cyclohexanol

[0361] A solution of 70 g (0.62 mol) of 30% aqueous hydrogen peroxide isadded dropwise over 2.75 hours to a mixture of 32.4 g (0.063 mol) ofbis(1-oxyl-2,2,6,6-tetramethylpiperidin-yl) sebacate and 5.0 g (0.025mol) of ferrrous chloride tetrahydrate in 100 g of cyclohexanol. Thereaction temperature is maintained at 40-45° C. during the addition. Thereaction mixture is then stirred at 40° C. for five hours and duringthis time, fresh 50% aqueous hydrogen peroxide (5.0 g, 0.074 mol) isadded to the reaction mixture in two equal portions. The following day,the reaction mixture is heated to 40° C., another portion of 50% aqueoushydrogen peroxide (2.5 g, 0.037 mol) is added, and the mixture ismaintained at 40° C. for another five hours. A solution of 100 g of 20%aqueous sodium sulfite is added to the mixture and the reactiontemperature is maintained at 70° C. for 45 minutes to decompose excesshydrogen peroxide. The combined organic layers are concentrated to give151 g of crude product. Water is added, and residual cyclohexanol isremoved by steam distillation. The remaining 50 g of crude product ispurified by flash chromatography on silica gel with a 10:1:10 partmixture of ethyl acetate:ethanol:hexane to afford 32.9 g of an oil.

[0362] NMR analysis shows that the oil containsbis[1-(trans-2-hydroxycyclohexyloxy)-2,2,6,6-tetra-methylpiperidin-4-yl]sebacate in addition to other structural isomers of said sebacatecompound.

EXAMPLE 4 Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith Cyclohexanol

[0363] A solution of 50 g (0.74 mol) of 50% aqueous hydrogen peroxide isadded dropwise over a 1.75 hour period to a mixture of 35.0 g (0.20 mol)of 4-hydroxy-1-oxyl-2,2,6,6-tetra-methylpiperidine and 10.0 gr (0.050mol) of ferrous chloride tetrahydrate in 100 g of cyclohexanol. Thereaction temperature is maintained at approximately 40-45° C. throughoutthe addition. After the peroxide addition is complete, the reactionmixture is stirred at 40° C. for five hours. The mixture is cooled toroom temperature and a solution of 100 g of 20% aqueous sodium sulfiteis added. The reaction miture is carefully heated at 60° C. for one hourto decompose excess peroxide. After acetone is added to the organiclayer, the crude product mixture is filtered to remove solids and thefiltrate is concentrated. Water is added and residual cyclohexanol isremoved by steam distillation. The crude product is purified by flashchromatography on silica gel with 2:1 (vlv) hexane/ethyl acetate toafford 36.3 g of a yellow oil.

[0364] Analysis by mass spectrometry shows the oil to be a mixture ofisomers of1-(hydroxycyclo-hexyloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine and1-(dihydroxycydohexyloxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine.

EXAMPLE 5 Reaction of 2,4-Bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-6-chloro-s-triazine with Cyclohexanol

[0365] A solution of 30 g (0.44 mol) of 50% aqueous hydrogen peroxide isadded over a 2 hour period to a mixture of 39.4 g (0.070 mol) of2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-6chloro-s-triazineand 7.0 g (0.035 mol) of ferrous chloride tetrahydrate in 150 g ofcyclohexanol at a temperature of 40-45° C. The reaction mixture isstirred at 40° C. for ten hours after the peroxide addition is complete,and during this time, another 19 g (0.28 mol) portion of 50% aqeuoushydrogen peroxide is added. Another portion of 50% aqueous hydrogenperoxide (25 g, 0.37 mol) is added while the reaction mixture is heatedat 50-65° C. for four hours. The reaction mixture is treated with asolution of 100 g of 20% aqueous sodium sulfite at 60° C. for one hourto decompose residual peroxide. The organic layer is concentrated to abrown oil which is extracted thrice with cyclohexane and once with ethylacetate. The combined extracts are concentrated to afford 43.4 g of ayellow solid.

EXAMPLE 62,4-Bis{N-[1-(trans-2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-(2-hydroxyethyl)amino-s-triazine

[0366] The product obtained in Example 5 is reacted with ethanolamineand sodium hydroxide solution. The crude reaction mixture is dulutedwith ethyl acetate and washed with water. The aqueous layer is extractedwith ethyl acetate, and the combined organic layers are concentrated.The residue is dissolved in ethyl acetate and cyclohexane is added. Abrown oil is removed. The remaining solution is concentrated to give13.7 g of crude product. The crude product is purified by flashchromatography on silica gel with 2:1 (v/v) ethyl acetate/hexane andthen 8:1 (v/v) ethyl acetate/methanol to afford 6.4 g of a yellow oil.The oil is dissolved in ethanol and treated with decolorizing carbon at60° C. for one hour. Solids are removed by filtration and the solvent isevaporated to give 6.5 g of an off-white solid, melting at 67-80° C.

[0367] NMR analysis shows the solid contains the title compound inaddition to a mixture of hydroxy-cyclohexyloxy and dihydroxycydohexyloxystructural isomers.

EXAMPLE 7Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Adipate

[0368] Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethyl-pieridin-4-yl) adipate and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 8Bis[1[-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Glutarate

[0369] Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6tetramethyl-pieridin-4-yl) glutarate and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 9Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Succinate

[0370] Aqueous hydrogen peroxide is-added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethyl-pieridin-4-yl) succinate and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 10Bis[1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Sebacate

[0371] Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethyl-pieridin-4-yl) sebacate and ferrouschloride tetrahydrate in phenethyl alcohol at 30-50° C. Excess peroxideis decomposed with aqeuous sodium sulfite solution. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford the title compound.

EXAMPLE 112,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-chloro-s-triazine

[0372] A total of 40 g (0.59 mol) of 50% aqueous hydrogen peroxide isadded in two portions over five hours to a mixture of 43.2 g (0.076 mol)of2,4-bis[N-(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl)butylamino-6-chloro-s-triazineand 7.0 g (0.035 mol) of ferrous chloride tetrahydrate in 150 g oftert-butyl alcohol and 15 g of water. Another portion of 50% aqueoushydrogen peroxide (3 g, 0.044 mol) is added to the reaction mixturewhile the temperature is maintained at 40-45° C. for 2.25 hours. Thereaction mixture is diluted with 100 g of ethyl acetate. A solution of100 g of 20% aqueous sodium sulfite is added and the reaction mixture isheated at 60° C. for one hour to decompose residual peroxide. Theaqueous layer is extracted with ethyl acetate, and the combined organiclayers are concentrated. The crude product is purified by flashchromatography on silica gel with 1:1 (v/v) hexane/ethyl acetate toafford 54.1 9 of the title compound.

EXAMPLE 122,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetramethylpiperidin-4-yl]butylamino}-6(2-hydroxyethyl)amino-s-triazine

[0373] The title compound is prepared by the reaction of theintermediate prepared in Example 11 with ethanolamine and sodiumhydroxide. The aqueous layer is removed, and the remaining layer isextracted with cyclohexane. Solvent is evaporated at reduced pressure,and the crude product is purified by flash chromatography on silica gelwith 1:2 (v/v) hexane/ethyl acetate to afford 4.1 g of the titlecompound as a white solid, melting at 110-120° C.

[0374]¹Hnmr (CDCl₃): δ=3.54 ppm (q,2H, NCH₂); 3.59 ppm (s,4H, NOCH₂).

EXAMPLE 13 Reaction of the Product of Example 11 withN,N′-Bis(3-aminopropyl)ethylenediamine

[0375] The product prepared in Example 11 is reacted withN,N′-bis(3-aminopropyl)ethylene-diamine in a 3:1 molar ratio. Theproduct mixture includesN,N′,N″-tris(2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-ly}-3,3′-ethylene-diiminodipropylamineandN,N′,N″′-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.

EXAMPLE 142,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-octylamino-s-triazine

[0376] The reaction of the compound prepared in Example 11 with excessoctylamine yields the title compound as an off-white glass melting at68-86° C.

EXAMPLE 15N,N′-Bis{4,6-bis(N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazin-2-yl}-1,6-diaminohexane

[0377] The title compound is prepared by the reaction of the compoundprepared in Example 11 with hexamethylenediamine.

EXAMPLE 16A Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith tert-Butyl Alcohol

[0378] A solution of 50% aqueous hydrogen peroxide is added to a mixtureof 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloridetetrahydrate in tert-butyl alcohol at 30-60° C. Excess peroxide isdecomposed with aqeuous sodium sulfite. The organic layer isconcentrated and the crude product is purified by flash chromatographyon silica gel to afford a sample of4hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

EXAMPLE 16B1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ylMethacrylate

[0379] The title compound is prepared by reaction of the compoundprepared in Example 16A with methyl methacrylate.

EXAMPLE 174-Allyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

[0380] The title compound is prepared by the reaction of the compoundprepared in Example 16A with allyl bromide.

EXAMPLE 184-(2,3-Epoxypropoxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

[0381] The title compound is prepared by the reaction of the compoundprepared in Example 16A with epichlorohydrin.

EXAMPLE 191-(2-Hydroxy-2-methylpropoxy)-2,2,6,6tetramethyl-piperidin-4-yl3-{[[[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yloxy]carbonyl]-amino]methyl}-3,5,5-trimethylcyclohexylcarbamate

[0382] The title compound is prepared by the reaction of the compoundprepared in Example 16A with5isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (=isophoronediisocyanate).

EXAMPLE 20Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]1,6-Hexanedicarbamate

[0383] The title compound is prepared by the reaction of the compoundprepared in Example 16A with hexamethylene diisocyanate.

EXAMPLE 211-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl Acrylate

[0384] The title compound is prepared by the reaction of the compoundprepared in Example 16A with methyl acrylate.

EXAMPLE 222,4,6-Tris{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazine

[0385] A solution of 40 g (0.35 mol) of 30% aqueous hydrogen peroxide isadded over 1.25 hours to a mixture of 11.7 g (0.011 mol) of2,4,6-tris[N-(1-oxyl-2,2,6,6tetramethylpiperidin-4-yl]butylamino}-s-triazineand 3.0 g (0.015 mol) of ferrous chloride tetrahydrate in 100 9 oftert-butyl alcohol and 9 g of water. The reaction temperature ismaintained at 60-65° C. during the peroxide addition. Two equal portions(2 g, 0.29 mol) of 50% aqueous hydrogen peroxide are added to thereaction mixture while the temperature is maintained at 60° C. for 9.5hours. After the reaction mixture is diluted with ethyl acetate andcooled to room temperature, a solution of 100 g of 20% aqueous sodiumsulfite is added. The reaction mixture is heated at 60° C. for one hourto decompose the excess peroxide. The aqueous layer is extracted withethyl acetate, and the combined organic layers are concentrated. Thecrude product is purified by flash chromatography on silica gel with 2:1(v/v) cyclohexane/ethyl acetate to afford a material which is trituratedwith 1:1 (v/v) cyclohexane/acetone to give 4.0 g of the title compoundas a white solid, melting at 172-176° C.

EXAMPLE 23A Reaction of 1-Oxyl-2,2,6,6-tetramethyl-piperidin-4-one withtert-Butyl Alcohol

[0386] Aqueous hydrogen peroxide is added to a mixture of1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one and ferrous chloride intert-butyl alcohol at 30-60° C. Excess peroxide is decomposed withaqueous sodium sulfite. The organic layer is concentrated and theresidue is purified by flash chromatography to afford the desired1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-one.

EXAMPLE 23B4-Butylamino-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

[0387] A mixture of butylamine, the compound prepared in Example 23A anda catalytic amount of 5% platinum on carbon is hydrogenated at 3atmospheres using a Parr apparatus. The catalyst is removed byfiltration, and the solvent is evaporated to afford the title compound.

EXAMPLE 244-Trimethylsilyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

[0388] The title compound is prepared by the reaction of the compoundprepared in Example 16A with chlorotrimethylsilane.

EXAMPLE 254-Benzoyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine

[0389] A solution of 50% aqueous hydrogen peroxide is added slowly to amixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-60° C. Excess peroxideis decomposed by aqueous sodium sulfite solution. The organic layer isconcentrated and the residue is purified by flash chromatography toafford the title compound.

EXAMPLE 261-(2-Hydroxy-2-methylpropoxy)4-[3-(trimethyl-silyl)propoxy]-2,2,6,6-tetramethylpiperidine

[0390] The title compound is prepared by reacting the compound preparedin Example 17 with trimethylsilane and hydrogen hexachloroplatinate(IV)in isopropyl alcohol.

EXAMPLE 27Tetrakis{3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yloxy]propy}-1,3,5,7-tetramethylcyclotetrasiloxane

[0391] The title compound is prepared by the reaction of the compoundprepared in Example 17 with 1,3,5,7-tetramethylcyclotetrasiloxane,hydrogen hexachloroplatinate(IV) in isopropyl alcohol.

EXAMPLE 28Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin4-yloxy]propyl]methyl}silane

[0392] The title compound is prepared by the reaction of the compoundprepared in Example 17 with poly(methylsilane) and hydrogenhexachloroplatinate(IV) in isopropyl alcohol.

EXAMPLE 29Poly{[3-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yloxy]propyl]methyl}siloxane

[0393] The title compound is prepared by the reaction of the compoundprepared in Example 17 with poly(methylsiloxane) and hydrogenhexachloroplatinate(IV) in isopropyl alcohol.

EXAMPLE 30 Mixture ofBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]GlutarateandBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Adipate

[0394] A mixture of the compound prepared in Example 16A, DBE-2 dimethylester mixture (DuPont), and lithium amide is heated at reflux in xylene.Methanol is distilled from the reaction mixture. The reaction mixture isquenched with dilute mineral acid, and the organic layer is washed withwater and dried over anhydrous magnesium sulfate. The xylene solution isevaporated at reduced pressure to afford the title compound mixture.

EXAMPLE 30A Mixture ofBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Glutarate andBis[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Succinate

[0395] When the procedure of Example 30 is repeated with DBE-9 adimethyl ester mixture (DuPont), the title mixture is prepared.

EXAMPLE 31 Reaction ofBis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl]Sebacate with Neopentylalcohol

[0396] Aqueous hydrogenperoxide is added-to a mixture ofbis(1-oxyl-2,2,6,6tetramethyl-piperidin-4-yl) sebacate and ferrouschloride in neopentyl alcohol according to the procedure of Example 25.

EXAMPLE 32 Reaction of 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one withNeopentyl Glycol

[0397] Aqueous hydrogen peroxide is added to a mixture of1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one and ferrous chloride inneopentyl glycol according to the procedure of Example 25.

EXAMPLE 33 Reaction of 4Octadecanoyloxy-1-oxyl-2,2,6,6-piperidine withtert-Amyl Alcohol

[0398] Aqueous hydrogen peroxide is added to a mixture of4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrouschloride in tert-amyl alcohol according to the procedure of Example 25.

EXAMPLE 344-Benzoyloxy-1-(2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidine

[0399] Tributyltinhydride is added dropwise to a solution of2-bromocydohexanol and excess4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. Themixture is heated to facilitate reaction. The crude reaction mixture ispassed through silica gel with heptane and then heptane/ethyl acetate toafford the title compound as a mixture os cis/trans isomers.

EXAMPLE 354-Hydroxy-1(2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidine

[0400] The title compound is prepared by heating the compound preparedin Example 34 in a solution of potassium hydroxide in methanol.

EXAMPLE 36 Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith Propylene Glycol

[0401] Aqueous hydrogen peroxide is added to a mixture of4-benzoyloxy-1-oxyl-2,2,6,-tetra-methylpiperidine and ferrous chloridetetrahydrate in pmpylene glycol according to the procedure of Example25.

EXAMPLE 37 Reaction of 4-Benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidinewith Trimethylene Glycol

[0402] Aqueous hydrogen -peroxide is added to a mixture of4-benzoyloxy-1-oxyl-2,2,6,6-tetra-methylpiperidine and ferrous chloridetetrahydrate in trimethylene glycol according to the procedure ofExample 25.

EXAMPLE 38Bis[1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidin-4-yl]Sebacate

[0403] Tributyltin hydride is added dropwise to a solution of2-iodoethanol and excess bis(1-oxyl-2,2,6,6tetramethylpiperidin-4-yl)sebacate in chlorobenzene. The crude reaction mixture is passed throughsilica gel with heptane and then heptane/ethyl acetate to afford thetitle compound.

EXAMPLE 39 Reaction of Bis(1-oxyl-2,2,6,6tetramethyl-piperidin-4-yl)Sebacate with Isopropanol

[0404] Aqueous hydrogen peroxide is added to a mixture ofbis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate and ferrouschloride tetrahydrate in isopropanol according to the procedure ofExample 25.

EXAMPLE 40 Reaction of4-Benzoyloxy-1-oxyl-2,2,6,6-tetramethyl-piperidine with 1,4-Butanediol

[0405] Aqueous hydrogen peroxide is added to a mixtureof4-benzoyloxy-1-oxyl-2,2,6,6-tetra-methylpiperidine and ferrouschloride tetrahydrate in 1,4-butanediol according to the procedure ofExample 25.

EXAMPLE 41 Reaction of 4-Hexyloxy-1-oxyl-2,2,6,6-tetramethyl-piperidinewith Pinacol

[0406] Aqueous hydrogen peroxide is added to a mixture of4-hexyloxy-1-oxyl-2,2,6,6-tetra-methylpiperidine and ferrous chloridetetrahydrate in pinacol according to the procedure of Example 25.

EXAMPLE 42 Reaction of 1-Oxyl-2,2,6,6-tetramethyl-piperidin-4-one withGlycerol

[0407] Aqueous hydrogen peroxide is added to a mixture of1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one and ferrous chloridetetrahydrate in glycerol according to the procedure of Example 25.

EXAMPLE 43 Reaction of 4-Hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidinewith 2-Ethyl-1-hexanol

[0408] Aqueous hydrogen peroxideadded to a mixture of4-hydroxy-1-oxyl-2,2,6,6-tetra-methylpiperidine and ferrous chloridetetrahydrate in 2-ethyl-1-hexanol according to the procedure of Example25.

EXAMPLE 441-(2-Hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine

[0409] A mixture of the compound prepared in Example 16A, methylhexadecanoate and lithium amide is heated at reflux in xylene, Methanolis distilled from the reaction mixture. The reaction mixture is quenchedwith dilute mineral acid, and the organic layer is washed with water anddried over anhydrous magnesium sulfate. The xylene solution isevaporated at reduced pressure to afford the title compound.

EXAMPLE 44A1(4-Hexadecanoyloxy-2,2,6,6-tetramethyl-piperidin-1-yloxy)-2-hexadecanoyloxy-2-methylpropane

[0410] The title compound is prepared by the reaction of the compoundprepared in Example 16A with excess methyl hexadecanoate and a catalyticamount of lithium amide in xylene.

EXAMPLE 45 Reaction ofN,N′,N″,N″′-Tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylaminewith Cyclohexanol

[0411] A mixture of N, N′, N″,N″′-tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butyl-amino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylaminein cyclohexanol is reacted with aqueous hydrogen peroxide and ferrouschloride tetrahydrate according to the method of Example 4. A whitesolid melting at 133-175° C. is obtained.

EXAMPLE 46 Reaction of2,4,6Tris[N-(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl]butylamino}-s-triazinewith Cyclohexanol

[0412] A mixture of2,4,6-tris[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-s-triazineand cyclohexanol is reacted with aqueous hydrogen peroxide and ferrouschloride tetrahydrate according to the procedure of Example 4. A lightbrown oil is obtained.

EXAMPLE 47Bis[1-(3-hydroxypropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl]Sebacate

[0413] Tributyltin hydride is added dropwise to a solution of3-bromo-1-propanol and excessbis(1-oxyl-2,2,6,6tetramethylpiperidin-4-yl) sebacate in chlorobenzene.The mixture is heated to facilitate reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 48Bis[1-(12-hydroxy-1-dodecyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]Sebacate

[0414] Tributyltin hydride is added dropwise to a solution of12-bromo-1-dodecanol and excessbis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene.The mixture is heated to facilitate reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 49Bis[1-(2-hydroxypropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl]Sebacate

[0415] Tributyltin hydride is added dropwise to a solution of1-bromo-2-propanol and excessbis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene.The mixture is heated to facilitate reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 50 Reaction of the Product of Example 11 withN,N′-Bis(3aminopropyl)ethylenediamine

[0416] N,N′-Bis(3-aminopropyl)ethylenediamine and the product preparedin Example 11 are reacted in a 1:3.0 to 1:3.5 molar ratio. The productmixture includesN,N′,N″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-trazin-6-yl}-3,3′-ethylenediiminodipropylamine,and N,N′,N″,N′″-tetrakis{2,4bis[N-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.

EXAMPLE 51 N,N′,N″,N″′-Tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methyl-propoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine

[0417] The title compound is prepared by the addition of aqueoushydrogen peroxide to a mixture ofN,N′,N″,N″′-tetrakis{2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,ferrous chloride and tert-butyl alcohol according to the procedure ofExample 7.

EXAMPLE 52 Reaction of the Product of Example 11 with N,N′-Bis(3aminopropyl)ethylenediamine

[0418] N,N′-Bis(3-aminopropyl)ethylenediamine and the product preparedin Example 11 are reacted in a 1:4.0 molar ratio. The product mixtureincludesN,N′,N″-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,31-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,and N,N′,N′,N′″-tetrakis{2,4-bis[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine.

EXAMPLE 53A2-{N-[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6tetramethyl-piperidin-4-yl]butylamino}-4,6-dichloro-s-triazine

[0419] The compound prepared in Example 23B is reacted with an equimolaramount of cyanuric chloride and sodium bicarbonate at 0° C. to give thetitle compound.

EXAMPLE 53BN,N′-Bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamine

[0420] The title compound is prepared by the hydrogenation at 50 psi ofthe compound obtained in Example 23A, hexamethylenediamine, methanol anda catalytic amount of 5% platinum on carbon.

EXAMPLE 53C

[0421]N,N′-Bis{2-[N-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]butylamino]-4-chloro-s-triazin-6-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamine

[0422] The title compound is prepared by reaction of the two compoundsprepared in Examples 53A and 53B in a 2:1 molar ratio in xylene at60-80° C. with sodium hydroxide as the acid acceptor.

EXAMPLE 53D Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl

[0423] The compounds prepared in Examples 53B and 53C are mixed togetherin a 2:1 molar ratio in xylene solution at 100-160° C. with sodiumhydroxide as the acid acceptor. The reaction mixture is then treatedwith 2,4-bis(dibutylamino)-6-chloro-s-triazine under the same conditionsto give an oligomeric product having a low number (2, 4, 6, 8) ofrepeating units terminated by the 2 4-bis(dibutylamino)-s-triazinylmoieties as seen in the structure below.

EXAMPLE 54 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl

[0424] N,N′-Bis(2,2,6,6-tetramethypiperidin-4-yl)-1,6-hexanediamine andN,N′-bis{2-[N-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-4-chloro-s-trazin-6-yl}-N,N′-bis(2,2,6,6tetra-methylpiperidin-4-yl)-1,6-hexanediamineare mixed together in a 2:1 molar ratio in xylene at 100-160° C. withsodium hydroxide as the acid acceptor. The reaction mixture is thentreated with 2,4-bis(dibutylamino)-6-chloro-s-triazine under the sameconditions. The resulting mixture of oligomers is heated with tert-butylhydroperoxide and a catalytic amount of molybdenum trioxide in an inertsolvent such as 1,2-dichloroethane to form the corresponding N-oxylcompounds. Aqueous hydrogen peroxide in then added to the mixture of theN-oxyl compounds and ferrous chloride tetrahydrate in tert-butyl alcoholaccording to the procedure of Example 7. The final products is a mixtureof oligomers as in Example 53D although the ratios of the individualcomponents may not be the same as in Example 53D.

EXAMPLE 55 Oligomer ofN-}2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinA-4-yl]-1,6-hexanediamineterminated with2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-butylamino-s-triazin-6-yl

[0425] The tile compound is prepared by heating a mixture of thecompounds prepared in Examples 53A and 53B, in a 1.33 to 1.0 molar ratioin xylene at 100-160° C. using sodium hydroxide as the add acceptor.Dibutylamine is then added to the reaction mixture under the sameconditions to complete the reaction. The product is a mixture ofoligomers that include 1-4 repeating units as seen in the structurebelow.

EXAMPLE 56 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-butylamino-s-triazin-6-yl

[0426] The title compound is prepared by heating a mixture of thecompounds prepared in Examples 53B and 53C, in a 0.5:1 molar ratio inxylene at 100-160° C. using sodium hydroxide as the acid acceptor.Dibutylamine is then added to the reaction mixture under the sameconditions to complete the reaction. The product is a mixture ofoligomers that include 1, 3, 5 and 7 repeating units as seen in thestructure below.

EXAMPLE 57 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetra-methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with2-butylamino-4-{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ly]-butylamino-s-triazin-6-yl

[0427] N,N′-Bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine andN,N′-bis{2-[N-(2,2,6,6-tetramethylpipeddin-4-yl)butylamino]-4-chloro-s-triazin-6-yl}-N,N′-bis(2,2,6,6-tetra-methylpiperidin-4-yl)-1,6-hexanediamineare mixed together in a 0.5:1 molar ratio in xylene at 100-160° C. withsodium hydroxide as the acid acceptor. The reaction mixture is thentreated with dibutylamine under the same conditions. The resultingmixture of oligomers is treated with tert-butyl hydroperoxide and acatalytic amount of molybdenum trioxide in an inert solvent such as1,2-dichloroethane to form the corresponding N-oxyl compounds. Aqueoushydrogen peroxide in then added to a mixture of the N-oxyl compounds andferrous chloride tetrahydrate in tert-butyl alcohol according to theprocedure of Example 7. The final product is a mixture of oligomers suchas prepared in Example 56 although the ratios of the individualcomponents may not be the same as those in the product of Example 56.

EXAMPLE 58 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6tetra-methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-1,6-hexanediamineterminated with Acetyl

[0428] The compounds prepared in Examples 53B and 53C are mixed togetherin a 2:1 molar ratio in xylene at 100-160° C. using sodium hydroxide asthe acid acceptor. After the reaction is complete, the reaction mixtureis concentrated at reduced pressure. Acetic anhydride is added to thereaction mixture at room temperature, and the mixture is then heated at130° C. The crude mixture is cooled and neutralized with potassiumcarbonate. The reaction mixture is concentrated at reduced pressure. Theproduct is a mixture of oligomers that include 2, 4, and 6 repeatingunits as seen in the structure below.

EXAMPLE 59 Oligomer ofN-{2-[N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetra-methylpiperidin-4-yl]butylamino]-s-triazin-4-yl}-N,N′-bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4yl]-1,6-hexanediamineterminated with Acetyl

[0429] Example 54 is repeated except that acetic anhydride is used inplace of 2,4-bis(dibutyl-amino)-6-chloro-s-triazine according to theprocedure of Example 58. The final product is a mixture of oligomers asdescribed in Example 58 although the ratios of the components may not beidentical to those of the product prepared in Example 58.

EXAMPLE 60Poly[-(2-hydroxy-2-methylpropoxy)-2,2,6-tetramethylpiperdin-4-ylMethacrylate

[0430] The title compound is prepared from the free radicalpolymerization of the compound obtained in Example 16B. The averagemolecular weight of the polymer is 1500-3000 amu.

EXAMPLE 61Poly[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ylAcrylate

[0431] The title compound is prepared from the free radicalpolymerization of the compound obtained in Example 21. The averagemolecular weight of the polymer is 1500-3000 amu.

EXAMPLE 62 1,4-Bis(4hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-butanol

[0432] Tributyltin hydride is added dropwise to a solution of1,4-dibromo-2-propanol and excess4-hydroxy-1-oxyl-2,2,6,8tetramethylpiperidine in chlorobenzene. Themixture is heated to facilitate the reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptane/ethyl acetateto afford the title compound.

EXAMPLE 63 1,3-Bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-propanol

[0433] Tributyltin hydride is added dropwise to a solution of1,3-dibromo-2-propanol and excess4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. Themixture is heated to facilitate the reaction. The crude reaction mixtureis passed through silica gel with heptane and then heptanelethyl acetateto afford the title compound.

EXAMPLE 64 2-Hydroxy-2-methylpropane-1,3-diylbis{[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl](1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)Sebacate

[0434] The title compound is isolated by high pressure liquidchromatography from the crude reaction product obtained in Example 2.

EXAMPLE 65 1,3-Bis(4-octadecanoyloxy-2,2,6,6tetramethylpiperidin-1-yloxy)-2-methyl-2-propanol

[0435] Aqueous hydrogen peroxide is added to a mixture of4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrouschloride tetrahydrate in tert-butyl alcohol at 30-50° C. Excess peroxideis decomposed with aqueous sodium sulfite solution. The organic layer isconcentrated to obtain a mixture which includes1-(2-hydroxy-2-methylpropoxy)-4-octa-decanoyloxy-2,2,6,6-tetramethylpiperidineand the title compound. The title compound is separated from the mixtureby high pressure liquid chromatography.

EXAMPLE 66 1,3-Bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-methyt2-propanol

[0436] The title compound is isolated by high pressure liquidchromatography from the crude reaction product obtained in Example 16A.

EXAMPLE 67 1,3-Bis(4-oxo-2,2,6,6tetramethylpiperidin-1-yloxy)-2-methyl-2-propanol

[0437] The title compound is isolated by high pressure liquidchromatography from the crude reaction product obtained in Example 23A.

EXAMPLE 681-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-ylHexanoate

[0438] The title compound is prepared by heating a mixture of methylhexanoate, the compound prepared in Example 16A, lithium amide andxylene at reflux while methanol is removed by distillation.

EXAMPLE 694-Benzoyloxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine

[0439] Tributyltin hydride is added dropwise to a solution of2-iodoethanol and 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine inchlorobenzene. The crude reaction mixtuire is passed through silica gelwith heptane and then heptanelethyl acetate to afford the fitlecompound.

EXAMPLE 70 4-Hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidine

[0440] The title compound is prepared by heating a methanolic solutionof the compound obtained in Example 69 with potassium hydroxide.

EXAMPLE 71Poly[4-hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetramethylpiperidin-4-ylsuccinate]

[0441] The title compound is prepared by the reaction of approximatelyequimolar amounts of dimethyl succinate and the compound prepared inExample 70.

EXAMPLE 72Poly[-4-hydroxy-1-(2-hydroxycyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-ylsuccinate]

[0442] The title compound is prepared by the reaction of approximatelyequimolar amounts of dimethyl succinate and the compound prepared inExample 35.

EXAMPLE 731-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6tetramethylpiperidine

[0443] A mixture of methyl stearate, the compound prepared in Example16A and a catalytic amount of lithium amide is heated at reflux inxylene. Methanol is distilled from the reaction mixture. The reaction isquenched with dilute acid. The organic layer is concentrated and thecrude product is purified by flash chromatography on silica gel toafford the title compound as a white solid melting at 51-56° C.

EXAMPLE 73A 1-(4-Octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane

[0444] The title compound is prepared by the reaction of the compoundprepared in Example 16A with excess methyl stearate and a catalyticamount of lithium amide in xylene.

EXAMPLE 744-Hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine

[0445] The title compound is prepared by heating a methanolic solutionof the compound obtained in Example 10 with potassium hydroxide.

EXAMPLE 75Poly[4-hydroxy-1-(2-hydroxy-1-phenylethoxy)-2,2,6,6-tetramethylpiperidin-4-ylsuccinate]

[0446] The title compound is prepared by the reaction of approximatelyequimolar amounts of dimethyl succinate and the compound-obtained inExample 74.

EXAMPLE 76 Stabilization of Thermoplastic Olefins

[0447] Molded test specimens are prepared by injection moldingthermoplastic olefin (TPO) pellets containing pigments, a phosphite, aphenolic antioxidant or hydroxylamine, a metal stearate, ultravioletlight absorbers or a hindered amine stabilizer or a mixture of UVabsorber and hindered amine stabilizer.

[0448] Pigmented TPO pellets are prepared from pure pigment or pigmentconcentrate, coadditives and commercially available TPO by mixing thecomponents in a Superior/MPM 1″ single screw extruder with a generalall-purpose screw (24:1 L/D) at 400° F. (200° C.), cooled in a waterbath and pelletized. The resulting pellets are molded into 60 mil (0.006inch), 2″×2″ plaques at about 375° F. (190° C.) on a BOY 30M InjectionMolding Machine.

[0449] Pigmented TPO formulation composed of polypropylene blended witha rubber modifier where the rubber modifier is an in-situ reactedcopolymer or blended product containing copolymers of propylene andethylene with or without a ternary component such as ethylidenenorbornene are stabilized with a base stabilization system consisting ofan N,N-dialkylhydroxyl-amine or a hindered phenolic antioxidant with orwithout an organophosphorus compound.

[0450] All additive and pigment concentrations in the final formulationare expressed as weight percent based on the resin.

[0451] Formulation contained thermoplastic olefin pellets and one ormore of the following components:

[0452] 0.0 to 2.0% pigment,

[0453] 0.0 to 50.0% talc,

[0454] 0.0 to 0.1% phosphite,

[0455] 0.0 to 1.25% phenolic antioxidant,

[0456] 0.0 to 0.1 % hydroxylamine

[0457] 0.05 to 0.10 calcium stearate,

[0458] 0.0 to 1.25% UV absorber

[0459] 0.0 to 1.25% hindered amine stabilizer.

[0460] The components are dry-blended in a tumble dryer prior toextrusion and molding.

[0461] Test plaques are mounted in metal frames and exposed in an AtlasCi65 Xenon Arc Weather-Ometer at 70° C. black panel temperature, 0.55W/m² at 340 nonometers and 50% relative humidity with intermittentlight/dark cycles and water spray (Society of Automotive Engineers-SAE J1960 Test Procedure). Specimens are tested at approximately 625kilojoule intervals by performing color measurements on an Applied ColorSystems spectrophotometer by reflectance mode according to ASTM D2244-79. Data collected include delta E, L*, a* and b* values. Glossmeasurements are conducted on a BYK-Gardner Haze/Gloss Meter at 60°according to ASTM D 523.

[0462] UV Exposure Testing

[0463] Test speciments exposed to UV radiation exhibit exceptionalresistance to photodegration when stabilized with light stabilizersystems comprising a combination of2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (TINUVIN® 328,Ciba), the compound of Example 73 andN,N′,N″,N″′-tetrakis[4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4yl)amino)-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane(CHIMASSORB® 119, Ciba). The control sample consists of a stabilizerformulation commonly used in the industry to impart UV stability. All ofthe samples contain a pigment, Pigment Red 177, and talc.

[0464] The test plaques described earlier contain the following (allconcentrations are weight percent based on resin):

[0465] Polymer substrate is commercially available polyolefin blendPOLYTROPE® TPP 518-01 supplied by A. Schulman Inc. Akron, Ohio)

[0466] Color package is 0.025% Red 3B -Pigment Red 177, C.l. #65300.

[0467] Each plaque contains:

[0468] 0.2% TINUVIN® 328;

[0469]0.1% calcium stearate; and

[0470] 15% talc.

[0471] The Control plaques additionally contain

[0472] 0.1% IRGANOX® B225 (50:50 blend of IRGANOX® 1010, Ciba(neopentanetetrayl tetrakis(4hydroxy-3,5di-tert-butylhydrocinnamate) andIRGAFOS® 168, Ciba [tris-(2,4di-tert-butylphenyl) phosphite;

[0473] 0.2% TINUVIN® 770, Ciba [bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate];

[0474] 0.2% CHIMASSORB 944, Ciba [polycondensation product of4,4′-hexamethylene-bis(amino-2,2,6,6tetramethylpiperidine) and2,4dichlo-6-tert-octylamino-s-triazine].

[0475] The two test plaques (NOR-1 and NOR-2) each contain 0.05%N,N,-dialkylhydroxylamine;

[0476] NOR-1 additionally contains

[0477] 0.2% of CHIMASSORB® 119; and

[0478] 0.2% of TINUVI® 123, Ciba,[bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate].

[0479] NOR-2 additionally contains

[0480] 0.2% of CHIMASSORB® 119; and

[0481] 0.2% of the compound of Example 73.

[0482] The results of the UV testing are given in the table below. DE*Gloss Value % Gloss Value 0 3000 0 3000 0 3000 Sample Kj/m² Kj/m² Kj/m²Kj/m² Kj/m² Kj/m² control 0.0 4.7 66.6 5.4 100 8.1 NOR-1 0.0 4.0 65.516.9 100 25.8 NOR-2 0.0 3.8 64.9 45.3 100 69.8

[0483] The compound of Example 73 present in test plaques NOR-2specifically shows greatly improved gloss retention compared to the lesseffective control system and in fact is also more effective that arelated hindered amine compound (TINUVIN® 123) present in test plaquesNOR-1. Resistance to color change upon UV exposure is also enhanced.

[0484] Polymer blends containing an unsaturated ternary component, suchas EPDM blends, are especially benefited with the more efficient instantlight stabilizer systems described above.

[0485] In all cases, the light stabilized formulations show much greatedresistance to photodegradation than unstabilized specimens which failquickly under the UV exposure conditions outlined above.

EXAMPLE 77 Paintable TPO

[0486] Molded test specimens are prepared by injection moldingthermoplastic olefin (TPO) pellets containing the instant compounds,pigments and other coadditives as described in

EXAMPLE 76.

[0487] The light stable formulations are painted with one-pack paintsystems and tested for TPO/paint interactions. Before painting, the testspecimens are first washed in accordance with GM998-4801 and dried for15 minutes at 200® F. (94° C.). Adhesion promoter is applied to the dryfilm thickness of 0.2-0.4 mils. The samples are dried for five minutesbefore a 1 K basecoat is applied to a film thickness of 1.2-1.4 mils.The painted panels are dried for three minutes, a clearcoat is thenapplied to a dry film thickness of 1.2-1.5 mils followed by ten minutesflash drying and a 30 minute oven bake at 250° F. (121° C.).

[0488] Paint adhesion is measured by Aggressive Adhesion Testing(proprietary test procedure conducted at Technical Finishing, Inc.) andTaber Scuff. Painted panels which retain greater than 80% of the paintfinish are considered acceptable. After Aggressive Adhesion Testing,samples with less than 5% paint loss are deemed acceptable.

[0489] Samples are tested to evaluate the TPO/paint interactions asfollows: Aggresive HALS Formulation* Taber Scuff Test Adhesion TestpK_(a) A 100% removed 6% Loss (fail) 9.1 B  0% removed 4% Loss (pass)4.6 C  0% removed 3% Loss (pass) 4.0

[0490] Formulation A contains 0.2% CHIMASSORB® 944, 0.2% TlNUVIN® 328,500 ppm calcium stearate and 750 ppm N,N-dialkylhydroxylamine inreactor-grade TPO.

[0491] A also contains 0.2% of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate (TlNUVIN® 770, pK_(a) of 9.1).

[0492] Formulations B and C contain 0.2% CHIMASSORB® 119, 0.2% TINUVIN®328, 500 ppm a calcium stearate and 750 ppm N,N-dialkylhydroxylamine inreactor-grade TPO.

[0493] B also contains 0.2% ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN®123, pK_(a) of 4.6).

[0494] C also contains 0.2% of1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetra-methylpiperidine(compound of Example 73, pK_(a) of 4.0)

[0495] The data in the table indicate that, although formulation Afailed in both the Taber Scuff and Aggressive Adhesion Tests, bothformulations B and C passed both paint adhesion tests. However, asinspection of the pK_(a) values attests, the lower the pK_(a) value(less basic) for the test hindered amine compound the less paint lossresults in this Aggressive Adhesion Test. The instant compound ofExample 73 having the hydroxyl moiety present has the lowest pK_(a)value and also the least paint loss even better than the close prior artcompound where no hydroxyl moiety is present.

EXAMPLE 78 Stabilization of Polypropylene Molded Articles

[0496] Molded test specimens are prepared by injection moldingpolypropylene pellets containing pigments, a phosphite, a phenolicantioxidant or hydroxylamine, a metal stearate, ultraviolet lightabsorbers or a hindered amine stabilizers or a mixture of UV absorbersand hindered amine stabilizers.

[0497] Pigmented polypropylene pellets are prepared from pure pigment orpigment concentrates, stabilizers, coadditives and commerciallyavailable polypropylene by mixing the components in a Superior/MPM 1″single screw extruder with a general all-purpose screw (24:1 UD) at 475°F. (250° C.), cooled in a water bath and pelletized. The resultingpellets are molded into 60 mil (0.06 inch thick) 2″×2″ plaques at about475° F. (250° C.) on a BOY 30M Injection Molding Machine.

[0498] Pigmented polypropylene formulations composed of polypropylenehomopolymer or polypropylene copolymer are stabilized with a basestabilization system consisting of an N,N-dialkylhydroxylamine or ahindered phenolic antioxidant with or without an organophosphorouscompound.

[0499] All additive and pigment concentrations in the final formulationsare expressed as weight percent based on the resin.

[0500] Formulations contained polypropylene pellets and one or more ofthe following components;

[0501] 0.0%-2.0% pigment,

[0502] 0.0%-50.0% talc,

[0503] 0.0%-50.0% calcium carbonate,

[0504] 0.0%-0.1% phosphite,

[0505] 0.0%-1.25% phenolic antioxidant,

[0506] 0.0%-0.1% hydroxylamine,

[0507] 0.05%-0.10% calcium stearate,

[0508] 0.0%-1.25% UV absorber,

[0509] 0.0%-1.25% hindered amine stabilizer.

[0510] The components are dry blended in a tumble dryer prior toextrusion and molding.

[0511] Test plaques are mounted in metal frames and exposed in an AtlasCi65 Xenon Arc Weather-o-meter at 70° C. black panel temperature, 0.55W/m² at 340 nanometers and 50% relative humidity with intermittentlight/dark cycles and water spray (Society of Automotive Engineers—SAE J1960 Test Procedure). Specimens are tested at approximately 625kilojoule intervals by performing color measurements on an Applied ColorSystems spectrophotometer by reflectance mode according to ASTM D2244-79. Data collected included delta E, L*, a* and b* values. Glossmeasurements are conducted on a BYK-GARDNER Haze/Gloss Meter at 60°according to ASTM D523.

[0512] UV Exposure Testina

[0513] Test specimens exposed to UV radiation exhibit exceptionalresistance to photodegradation when stabilized with light stabilizersystems comprised of a combination of Tinuvin 328, the compound ofExample 73 and CGL 2020. CGL 2020 is oligomer ofN{[2-(N-2,2,6,6-tetra-methylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamine terminated with 2,4bis(dibutylamino)-s-triazin-6-yl.The Control sample consists of a stabilizer formulation commonly used inthe industry to impart UV stability. All of the samples contain PigmentRed 177. % Gloss DE* Gloss Values Retention Red 3B Formulations 30003000 3000 Comp. 1 Comp. 2 Comp. 3 0 Kj/m² Kj/m² 0 Kj/m² Kj/m² 0 Kj/m²Kj/m² Control 0.14% 0.20% 0.2% Tin. 0 6.5 88% 24% 100% 28% T123 CGL 3282020 Ex. 73 0.10% Ex. 0.10% 0.1% Tin. 0 0.6 88% 77% 100% 88% 73 CGL 2020328 NOR 2 0.10% 0.10% 0.1% Tin. 0 8.2 87% 13% 100% 14% NOR 2 CGL 2020328

[0514] All additive and pigment concentrations in the final formulationsare expressed as weight percent on the resin.

[0515] The formulation containing the subject compound of Example 73specifically shows greatly improved gloss retention compared to the lesseffective Control stabilizer system even at a lower total concentration.Resistance to color change upon UV exposure is also significantlyenhanced. The subject compound of Example 73 is also significantly moreeffective in maintaining appearance when compared with another solidN—O—R HALS (NOR 2) of similar molecular at equal concentrations.

[0516] In all cases, the light stabilized formulations show much greaterresistance to photodegradation than unstabilized specimens which failquickly under the UV exposure conditions outlined above.

EXAMPLE 79 Polypropylene Fiber

[0517] Fiber samples are prepared by extruding fiber-grade polypropylenewith the instant compounds, coadditives and pigments. Typicalformulations contain the instant compounds at levels from 0.05 to 2.0%,a metal stearate such as calcium stearate at 0.05 to 0.5%, pigments from0 to 5%, UV absorbers at levels of 0.05 to 2.0%, phosphites at 0 to0.1%, phenolic antioxidants at 0 to 1.25%, N,N-dialkylhydroxylamines at0 to 0.1% and optionally other hindered amines at levels of 0 to 2.0%.All additive and pigment concentrations in the final formulations aregiven as weight percent based on the resin.

[0518] Pigment concentrates are prepared from pure pigment andpolypropylene (PROFAX®, Hercules) by mixing the two components in a highshear mixer in a ratio of 25% pigment and 75% resin, pressing theresulting resin/pigment mixture on a Wabash Compression molder (Model#30-1515-4T3) into a thin sheet and dividing the sheet into fine chipsfor dispersion in polypropylene at reduced concentrations. Altematively,pigment concentrates areobtained as pigment dispersions in a suitablecarrier resin for subsequent blending in fiber at reducedconcentrations.

[0519] Formulations containing polypropylene, 0.05-0.1% phosphite,0-1.25% phenolic antioxidant, 0-0.1% dialkylhydroxylamine, 0.05-0.1%calcium stearate, 0-1.25% UV absorber, 0-1.25% hindered amine are dryblended in a tumble dryer, extruded on a Superior/MPM 1″ single screwextruder with a general all-purpose screw (24:1 LID) at 475° F. (246°C.), cooled in a water bath and pelletized. The resulting pellets arespun into fiber at about 475° F. (246° C.) on a HILLS Research FiberExtruder (Model #REM-3P-24) fitted with a 41 hole, delta configuationspinneret. The spun tow is stretched at a draw ratio of 3.2:1 producinga final denier of 615/41.

[0520] Fiber samples are knitted into socks on a Lawson-HemphillFiberAnalysis Knitter, cut into appropriate lengths and exposed in an AtlasCi65 Xenon Arc Weather-O-meter at 89° C. black panel temperature, 0.55W/m² at 340 nanometers and 50% relative humidity (Society of AutomotiveEngineers—SAE J 1885 Test Procedure).

[0521] Fiber samples are tested by performing color measurements on anApplied Color Systems spectrophotometer by reflectance mode according toASTM D 2244-79. Identical, but separate, fiber samples are examined forcatastrophic failure and the time to failure is recorded.

[0522] The samples containing the instant compounds exhibit goodstabilization performance against the deleterious effects of UV light.

EXAMPLE 80

[0523] Other socks of propylene fiber as prepared in Example 79 areexposed in a Blue M forced draft oven at 120° C. Failure is determinedby the criterion set forth in Example 79. The longer it takes for thecatastrophic failure to occur, the more effective is the stabilizingsystem.

[0524] The socks containing the instant compounds exhibit good thermalstabilization efficacy.

EXAMPLE 81

[0525] Film grade polyethylene is dry blended with approximately 10% byweight of the test additives, such as the compound of Example 51, andthen melt compounded at 200° C. into “Masterbatch” pellets. The fullyformulated “Masterbatch” pellets are dry blended with polyethylene resinto get the desired final stabilizer concentrations. Typical formulationscontain the instant compounds at levels from 0.05% to 2.0%, a metalstearate such as calcium stearate at 0.05% to 0.5%, a phosphite at 0% to0.1%, a phenolic antioxidant at 0% to 1.25%, an N,N-dialkylhydroxylamineat 0% to 0.1% and optionally a hindered amine at 0% to 2.0%. The Thisstabilized fully formulated resin is then blown at 200° C. into a 150micron thick film on a DOLCI film line.

[0526] The blown films are exposed in an Atlas Xenon-Arc WeatherOmeteraccording to ASTM G26 at 63° C. bpt, 0.35 W/m² at 340 nm with no spraycycle. Films are tested periodically for any change in elongation usingan Instron 112 tensile tester. Failure in this test is determined byobservation of the loss of % elongation in the film. The longer it takesfor this loss to occur, th more effective is the stabilizer system.

[0527] The films containing the instant compound mixture show good lightstabilizing efficacy.

EXAMPLE 82

[0528] Film grade polyethylene is dry blended with 10% loading of thetest additives, such as the compound of Example 51, as described inExample 81, and then melt compounded at 200° C. into fully formulatedmaster batch pellets. The master batch pellets are dry blended with thepolyethylene resin to get the final stabilizer concentration. The fullyformulated resin is then blown at 200° C. into a 150 micron thick filmusing a DOLCI film line.

[0529] The resulting films are exposed on a greenhouse on galvanizediron backing. Treatment includes applications of pesticides on a regularbasis (i.e. sodium N-methyidithio-carbamate, VAPAM' every six months andSESMETRIN' every month). Performance is measured by monitoring thepercent residual elongation. Failure is defined as the time to a 50%loss of original elongation.

[0530] The films containing the instant compounds show good resistanceto pesticides.

EXAMPLE 83

[0531] Master batch pellets prepared as described in Example 81 are dryblended into polyethylene resin to get the final stabilizercocentrafion. The fully formulated resin is then blown at 200° C. into a25 micron thick film using a DOLCI film line.

[0532] The resulting films are exposed on a soil to simulateagricultural mulch film conditions. Treatment indudes exposure to methylbromide fumigant for three days at 60 g/m³. Performance is measured bymonitoring the time to physical embrittlement.

[0533] The films containing the instant compounds show good resistanceto fumigants.

EXAMPLE 84

[0534] Greenhouse film samples are prepared as described in Example 81,but in addition to the instant compounds also contain a metal stearateor a metal oxide. Typical formulations contain from 0.05 to 2% by weightof the instant hindered amines, 0.05 to 0.5% of a metal stearate such ascalcium oxide, and 0.05 to 0.5% of a metal oxide such as zinc oxide ormagnesium oxide.

[0535] Effectiveness is monitored as described in Example 82. The filmscontaining the instant compounds exhibit good light stability.

EXAMPLE 85

[0536] Polypropylene fiber is prepared as described in Example 79. Inaddition to the instant compounds, selected halogenated flame retardantsare also included in the formulation. The flame retardants aretris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate, decabromodiphenyloxide, ethylene bis-(tetrabromophthalimide), or ethylenebis-(dibromo-norbomane-dicarboximide).

[0537] Using the criterion for light stabilization described in Example79, the socks knitted from the polypropylene fiber containing theinstant compounds exhibit good light stability.

EXAMPLE 86

[0538] Molding grade polypropylene is dry blended with test additivesand then melt compounded into pellets. In addition to the instantcompounds, selected flame retardants are also included. The flameretardants are tris(3bromo-2,2-bis(bromomethyl)propyl)phosphate,decabromodiphenyl oxide, ethylene bis-(tetrabromophthalimide), orethylene bis-(dibromo-norbomanedicarboximide). The pelletized fullyformulated resin is then injection molded into test specimens using aBoy 50M laboratory model injection molder.

[0539] Test plaques are mounted in metal frames and exposed in an AtlasCi65 Xenon Arc Weather-Ometer with intermittent lightdark cycles andwater spray following the ASTM G26 test procedure. Specimens are testedat periodic intervals for changes in tensile properties. Failure in thistest is determined by the observation of the loss of tensile properties.The longer it takes for the loss in properties to occur, the moreeffective is the stabilizer system.

[0540] The test samples containing the instant compounds exhibit goodlight stabilization properties.

EXAMPLE 87

[0541] Molded test specimens are prepared by injection moldingthermoplastic olefin (TPO) pellets as described in Example 76. Inaddition to the instant compounds, selected flame retardants are alsoincluded in the test specimens. The flame retardants aretris(3bromo-2,2-bis(bromomethyl)propyl) phosphate, decabromodiphenyloxide, ethylene bis-(tetrabromo-phthalicmide), ethyenebis-(dibromo-norbomanedicarboxmide).

[0542] The samples including the instant hindered amines exhibit goodlight stabilizing activity.

EXAMPLE 88

[0543] Film grade polyethylene is compounded and blown into film at 200°C. as described in Example 82 using a DOLCI film line. In addition tothe instant compounds, selected flame retardants are included in theformulation. The flame retardants aretris(3bromo-2,2-bis(bromomethyl)propyl) phosphate, decabromodiphenyloxide, ethylene bis-(tetrabromo-phthalimide), or ethylenebis-(dibromo-norbomanedicarboximide).

[0544] When tested for light stabilizing activity as described inExample 82, the films containing the instant compounds exhibit goodstabilization.

EXAMPLE 89

[0545] Molded test specimens are prepared by injection moldingthermoplastic olefin (TPO) pellets containing the instant compounds,pigments and other coadditives as described in Example 77.

[0546] The test specimens are painted with one-pack paint systems andtested for TPO/paint interactions. Before painting, the test specimensare first wiped with isopropanol and air blasted to remove any dustAfter a five minute flash, these specimens are coated with the adhesionpromoter, then the base coat, and then optionally a clear coat Typicalfilm thickness of these various coatings are 0.1-0.3 mils for theadhesion promoter, 0.6-0.8 mils for the base coat, and 1.2-1.5 mils forthe clear coat. After painting, the specimens are cured in an over at120° C. for 30 minutes.

[0547] Samples are tested to evaluate the TPO/paint interactions asfollows: In the initial adhesion test, a clear cellophane adhesive tapeis used to pull on a 3 mm cross hatched paint surface or; in thehumidity test, the painted plaques are exposed for 240 hours at 38° C.in an atmosphere having 98% relative humidity. The blister rating istested by visual observation according to ASTM D 714.

[0548] The samples containing the instant compounds exhibit goodTPO/paint interaction properties as determined by the criteria above.

EXAMPLE 90 Thermoplastic Elastomers

[0549] Resin materials of the general class known as thermoplasticelastomers, examples of which include, copolymers of styrene withbutadiene or isoprene and/or ethylene-cobutylene such as SBS, SEBS andSIS, are dry blended with the instant compounds and melt compounded intopellets. Typical formulations contain the instant compounds at levelsfrom 0.05% to 2.0%, a metal stearate such as calcium stearate at 0.05%to 0.5%, pigments from 0% to 5%, UV absorbers at levels of 0.05% to2.0%, phosphites at 0.0%-0.1%, phenolic antioxidants at 0.0%-1.25%,N,N-dialkylhydroxylamine at 0.0%-0.1%, and optionally other hinderedamine stabilizers at levels of 0.0% to 2.0%.

[0550] The pelletized fully formulated resin is then processed into auseful article such as blown or cast extrusion into film; injectionmolded into a molded article; thermoformed into molded articles;extruded into wire and cable housing; or rotational molded into hollowarticles.

[0551] The materials containing the instant compounds exhibit stabilityagainst deleterious effects of UV light and thermal exposure.

EXAMPLE 91

[0552] Articles prepared according to Example 90 which additionallycontain selected organic pigments as well as the instant compounds alsoexhibit stability against the deleterious effects of actinic light andthermal exposure.

EXAMPLE 92

[0553] Articles prepared according to Example 90 which additionallycontain a hindered phenolic antioxidant selected from the groupconsisting of neopentanetetrayltetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate, octadecyl3,5-di-tert-butyl4hydroxyhydrocinnamate,1,3,5trimethyl-2,4,6tris(3,5,-di-tert-butyl-4-hydroxybenzyl)benzene,1,2-bis(3,5di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine,calcium [bis(monoethyl 3,5-ditert-butyl-4-hydroxybenzyl)-phosphonate],1,3,5tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and1,3,5tris(3-hydroxy-4-tert-butyl-2,6dimethylbenzyl) isocyanurate, aswell as the instant compounds also exhibit stability against thedeleterious effects of actinic light and thermal exposure.

EXAMPLE 93

[0554] Articles prepared according to Example 90 which additionallycontain an organophosphorus stabilizer selected from the groupconsisting of tris(2,4-di-tert-butylphenyl) phosphite,bis(2,4-di-tert-butylmethylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyl-tris-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], tetrakis(2,4di-butylphenyl) 4,4′-biphenylenediphosphonite,tris(nonylphenyl) phosphite, bis(2,4di-tert-butylphenyl) pentaerythrityldiphosphite, 2,2′-ethylidenebis(2,4di-tert-butylphenyl) fluorophosphiteand 2-butyl-2-ethylpropan-1,3-diyl 2,4,6-tri-tert-butylphenyl phosphiteas well as the instant compounds of also exhibit stability against thedeleterious effects of actinic light and thermal exposure.

EXAMPLE 94

[0555] Articles prepared according to Example 90 which additionallycontain a benzofuranone stabilizer which is5,7-di-tert-butyl-3-(3,4dimethylphenyl)-2H-benzofuran2-one, as well asthe instant compounds also exhibit stability against the deleteriouseffects of UV light and thermal exposure.

EXAMPLE 95

[0556] Articles prepared according to Example 90 which additionallycontain a dialkylhydroxylamine stabilizer which isN,N-dialkylhydroxylamine made by the direct oxidation ofN,N-di(hydrogenated tallow)amine as well as the instant compounds alsoexhibit stability against the deleterious effects of actinic light andthermal exposure.

EXAMPLE 96

[0557] Articles prepared according to Example 90 which additionallycontain other hindered amine stabilizers selected from the groupconsisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)-sebacate, thepolycondensation product of1-(2-hydroxyethyl)2,2,6,6tetramethyl-4-hydroxy-piperidine and succinicacid, N,N′,N,″,N″′-tetrakis[4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylenebis(amino-2,2,6,6tetramethylpiperidine) and2,4-dichloro-6tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexamethylenebis(amino-2,2,6,6tetramethyl-piperidine) and2,4-dichloromorpholino-s-triazine, 2,2,6,6-tetramethylpiperidin-4-yloctadecanoate,3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-pyrrolidin-2,5-dione,1,3,5-tris{N-cyclohexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino}-s-triazine,poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane, thepolycondensation product of2,4-dichloro-6-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino)-s-triazineand2,2′ethylene-bis{[2,4-(2,2,6,6tetramethylpiperdin-4-yl)butylamino-s-triazin-6-yl]amino-trimethyleneamino}as well as the instant compounds also exhibit stability against thedeleterious effects of actinic light and thermal exposure.

EXAMPLE 97

[0558] Articles prepared according to Example 90 which additionallycontain other N-hydrocarbyloxy substituted hindered amines selected fromthe group consisting of bis(1-octloxy-2,2,6,6-tetramethylpiperidin-6-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cydohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, and1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate as wellas the instant compounds also exhibit stability against the deleteriouseffects of actinic light and thermal exposure.

EXAMPLE 98

[0559] Articles prepared according to Example 90 which additionallycontain a o-hydroxy-phenyl-2H-benzotriazole, a hydroxyphenylbenzophenone or a o-hydroxyphenyl-s-triazine UV absorber selected fromthe group consisting of2-(2-hydroxy-3,5di-α-cumylphenyl)-2H-benzo-triazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4di-tert-butylphenyl 3,5-di-ert-butyl-4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone and2,4-bis(2,4dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine aswell as the instant compounds also exhibit stability against thedeleterious effects of UV light and thermal exposure.

EXAMPLE 99

[0560] The hindered amine test stabilizers are incorporated into atwo-component polyester urethane coating based on a commerciallyavailable polyester polyol (DESMOPHEN® 670-80) and commerciallyavailable isocyanurate (DESMODUR® N-3390) at a level of 2% by weightbased on total resin solids. The coating system is catalyzed with 0.015%dibutyl tin dilaurate based on total resin solids.

[0561] Each coating formulation is applied by drawdown onto transparentglass slides approximately 4″×6″ to a film thickness of about 2 mils(0.002″) in triplicate.

[0562] These triplicate glass plates are processed as seen below:

[0563] Plate 1—bake for 30 minutes at 180° F. (82° C.); age at roomtemperature; and observe daily.

[0564] Plate 2—allow to air dry (ambient cure); age at room temperature;and observe daily.

[0565] Plate 3—allow to air dry for one day; age in a 120® F. (49° C.)oven; observe daily and continue aging at 120° F. (49° C.).

[0566] Starting at time zero, all plates are evaluated for visualappearance, noting the development of any cloudiness within the coatingand any exudate on the surface of the coating. The results of four daysof observation are noted below. Sample* 0 Day 1 Day 2 Day 3 Day 4 18months Plate 1 A cl cl cl cl cl clear B sl h haze haze haze haze haze Ccl cl cl cl cl clear Plate 2 A cl cl cl cl cl clear B sl h haze hazehaze haze haze C cl cl cl cl cl clear Plate 3 A cl cl cl cl cl clear Bsl h haze haze haze haze haze C cl cl cl cl cl clear

[0567] These data show that the instant compound having a hydroxy moietypresent on the group attached to the 1-position of the hindered amineprovides excellent solubility and compatibility for the polyesterurethane coating that cannot be achieved with the closest prior artcompound where said hydroxy moiety is absent

[0568] Experience teaches that, if the instant compounds are soluble andcompatible in this particular clearcoat, they will certainly becompatible and soluble in other resin systems.

EXAMPLE 100

[0569] Approximately 50 mL of the same stabilized formulatedtwo-component clear coatings described in Example 99 are alilowed to gelin a sealed 4 ounce jar. The solidified coatings are visually observedfor clarity after solidification. The development of opacity orcloudiness is indicative of an incompatibility between the hinderedamine stabilizer and the formulated coating.

[0570] Solidified coating in jar Sample* 0 Day 1 Day 2 18 months A clearclear clear clear B clear cloudy cloudy cloudy C clear clear clear clear

[0571] These data show that the instant compound having a hydroxy moietypresent on the group attached to the 1-position of the hindered amineprovides excellent solubility and compatibility for the polyesterurethane coating that cannot be achieved with the closest prior artcompound where said hydroxy moiety is absent.

EXAMPLE 1011-(2-Hydroxy-2-methylpropoxy)-4-[-9-(methoxy-carbonyl)nonanoyloxy]-2,2,6,6-tetramethylpiperidine

[0572] The title compound is prepared by the reaction of the compoundprepared in Example 16A with one equivalent or more of dimethyl sebacateand a catalytic amount of lithium amide in xylene.

EXAMPLE 1021-(2-Hydroxy-2-methylpropoxy)-4-[5-(methoxycarbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine

[0573] The title compound is made by the procedure of Example 101 wheredimethyl sebacate is replaced by an equivalent amount of dimethyladipate.

EXAMPLE 1031-(2-Hydroxy-2-methylpropoxy)4-[3-(methoxycarbonyl)propionyloxy]-2,2,6,6-tetramethylpiperidine

[0574] The title compound is made by the procedure of Example 101 wheredimethyl sebacate is replaced by an equivalent amount of dimethylsuccinate.

EXAMPLE 1041-(2-Hydroxy-2-methylpropoxy)-4-[4-(methoxycarbon)butyryloxy]-2,2,6,6-tetramethylpiperidine

[0575] The title compound is made the procedure of Example 101 wheredimethyl sebacate is replaced by an equivalent amount of dimethylglutarate.

EXAMPLE 105 Condensation Product of4Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith Hexamethylene Diisocyanate, and Terminated with Methoxy

[0576] The title compound is prepared from the reaction of approximatelyequimolar amounts of the compound prepared in Example 16A withhexamethylene diisocyanate followed by reaction with excess methanol.

EXAMPLE 106 Condensation Product of4-Hydroxy-1-(2-hydroxyethoxy)-2,2,6,6-tetra-methylpiperidine withHexamethylene Diisocyanate, and Terminated with Methoxy

[0577] The title compound is prepared from the reaction of approximatelyequimolar amounts of the compound prepared in Example 70 withhexamethylene diisocyanate, followed by reaction with excess methanol.

EXAMPLE 107 Condensation Product of4-Hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine withHexamethylene Diisocyanate, and Terminated with Methoxy

[0578] The title compound is prepared from the reaction of approximatelyequimolar amounts of the compound prepared in Example 74 withhexamethylene diisocyanate, followed by reaction with excess methanol.

EXAMPLE 108 Stabilization of a Two-Component Acrylic Urethane Clearcoat

[0579] The hindered amine test stabilizers are incorporated into atwo-component acrylic urethane coating as described om Example 99. Thesystem is catalyzed with 0.02% by weight of dibutyltin dilaurate basedon the total resin solids. The stabilizers are added at the appropriatelevel to the acrylic polyol portion of the two-component coating whichis then combined with the isocyanate component immediately prior toapplication.

[0580] Steel panels 3″×4″ primed with an electrocoat primer are thencoated with a light blue metallic basecoat, then with the stabilizedclearcoat. The basecoat is spray applied to a thickness of 1.0 mil (25microns) dry film thickness and the stabilized clearcoat is then appliedto a thickness of 2.0 mils (50 microns) dry film thickness. The coatingis air-dried and aged for two weeks. The panels are then exposed in aXenon-Arc Weather-Ometer under the following conditions:

[0581] Cam 180 cycle: 40 minutes light only; 20 minutes light and frontspray; 60 minutes light only; 60 minutes dark and rear spray condensate.

[0582] Lamp filters are: quartz inner/borosilicate S outer.

[0583] Irradiance: 0.45 watts per square meter.

[0584] 20° Gloss is measured before exposure and at 500 hour intervalsduring exposure. Higher gloss retention is desirable. Percent Retentionof 20° Gloss Sample* 4500 hours 8500 hours 12000 hours A 17 — — B 60 22— C 47 17 — D 34 22 — E 41 23 — F 75 45 28 G 77 45 27

[0585] These data show that the instant hydroxy substituted compoundsgive comparable 20° Gloss Retention values to NOR compounds atequivalent molar concentrations.

EXAMPLE 109 Stabilization of a Two-Component Acrylic Urethane Clearcoat

[0586] A clearcoat as prepared in Example 108 is applied by spin-coatingto 1″ silicon disks to a dry film thickness of approximately 25 microns.The initial optical film thickness of each disk is measured using aZeiss interferometer. The disks are then exposed in a Xenon-ArcWeather-Ometer under the following conditions:

[0587] Cam 180 cycle: 40 minutes light only; 20 minutes light and frontspray; 60 minutes light only; 60 minutes dark and rear spray condensate.

[0588] Lamp filters are: quartz inner/quartz outer.

[0589] Irradiance: 0.55 wafts per square meter.

[0590] Optical film thickness is remeasured every 250 hours and filmloss is determined for each formulation. The film loss caused byweathering after 3972 and 5561 hours is tabulated in the table below. Alower value for film loss is desirable. Film Loss (in microns) Sample*3972 hours 5561 hours A 23.3  complete erosion B 6.9 16.3 C 6.7 17.8 D6.3 14.3 E 5.9 12.4 F 6.5 16.1 G 6.6 16.7

[0591] These data show that the instant hydroxy substituted compoundsgive comparable resistance to erosion as the closest NOR compounds atequivalent molar concentrations.

EXAMPLE 110 Coatings over Plastic Substrates

[0592] A major application for non-basic hindered amines is in theprotection of automotive topcoats applied over plastic substrates.However, many low molecular weight, non-reactable light stabilizersmigrate into the plastic substrate during drying and cure. As aconsequence, a significant portion of the light stabilizer may be lostfrom the topcoat into the substrate and hence be ineffective inprotecting said topcoat.

[0593] The extent of migration of hindered amine stabilizers duringapplication and cure of the coating is determined by comparing theconcentration of hindered amine in the cured dearcoat applied over aplastic substrate versus the same clearcoat applied over a non-permeablesubstrate such as glass or steel.

[0594] Hindered amine stabilizers under test are incorporated into aflexible thermoset acrylic/melamine clear coating appropriate for use onautomotive plastic substrates. The hindered amine is incorporated at alevel of 1.5% by weight based on total resins solids.

[0595] Each coating formulation is applied by an automatic sprayappratus onto automotive grade RIM (Reacting Injection Molded) substrateand TPO (thermoplastic polyolefin). Both substrates are in form of4″×12″ plaques. Each coating is applied to achieve a dry film thicknessof approximately 2.0 mils (50 microns). The coatings are cured by bakingat 250° F. (121° C.) for 20 minutes.

[0596] Triplicate samples of each cured coating formulation are removedfrom each substrate and cryoground to a fine powder. A known amount ofeach sample is extracted in refluxing toluene ovemight. The hinderedamine present is analyzed quantitatively by dilution to a known volumeand analyzed by HPLC or SFC chromatography. Calibration curves for eachtest stabilizer compound are developed. The hindered amine content ofeach extracted coating is determined by this method.

[0597] When the instant hindered armine compounds substituted on theN-atom with an —O—E—OH moiety are compared to the corresponding —NORcompounds lacking such a hydroxyl moiety, a higher percent recovery ofthe instant hindered amine compound from the dearcoat over a plasticsubstrate is found indicating that much less of the instant hinderedamine stabilizer migrates into the plastic substrate allowing for betterstabilization of the clear topcoat over such plastic substrates.

EXAMPLE 111 Stabilization of Waterborne Wood Varnish

[0598] Waterborne coating comprise a significant and increasingproportion of the coating in use for a wide variety of applicationsincluding automotive basecoats, industrial coatings and trade salecoatings. These coatings may be pigmented or transparent. The trends arealso towards higher solids formulation which in general depend on lightstabilizers to maintain properties on exterior exposure, and towardslower levels of cosolvents. This requires higher solubility ofstabilizers in such cosolvents (primarily water) or actual solubility inwater.

[0599] The test stabilizers are incorporated into a waterbornedispersion by predissolution in a cosolvent blend. The waterbornedispersion is a commercially available acrylic/urethane hydrid resin.The cosolvent blend is a 1:1 mixture of TEXANOL®(2,2,4-trimethyl-1,3pentanediol, Texaco) and ARCOSOLVE® TPM(tripropylene glycol methyl ether, AtlanticRichfield).

[0600] 0.45 gram of the test stabilizer is predissolved in 10 g of thecosolvent blend which is then incorporated into the followingcomposition: ppw FLEXTHANE ® 630 (Air Products) 100.0  Foamaster VF 0.1Water 10.0  TEXANOL/ARCOSOLVE/hindered amine 10.5  UV absorber(TINUVIN ® 1130, Ciba) 1.2 BYK 348 0.5 MICHEMLUBE ® 162 2.0

[0601] Each coating is brush applied onto 6″×6″ sections of cedar andpine boards. The weight of the coating applied is regulated by weighingthe coating and brush before and after application and ensuring that thesame weight of coating is applied to each section.

[0602] The coated board sections are allowed to dry at ambienttemperature for two weeks, then evaluated for visual appearance, glossand Hunter L*, a* and b* color. The sections are exposed on racks at a45° angle in South Florida for six months before being returned andevaluated for visual appearance, gloss, color change and any other signsof degradation or delamination.

[0603] The instant hindered amine compounds substituted on the N-atomwith an —C—E—OH moiety provide better stabilization efficacy to thesections in respect to visual appearance, gloss retention, resistance tocolor change and to delamination than do the corresponding —NORcompounds lacking such a hydroxyl moiety.

EXAMPLE 112 Stabilization of Pigmented Automotive OEM Basecoat

[0604] A basecoat pigmented with a mixture of Pigment Red 177 and micais stabilized with 1% by weight of a hindered amine stabilizer based onthe total basecoat solids (pigment plus resin). The basecoat is sprayapplied at a dry film thickness of 1 mil (25 microns) to primed 4″×12″steel panels, then topcoated with a high solids commercially availableautomotive clearcoat. The coated panels are cured in an over at 250° F.(121° C.) for 30 minutes. The panels are then exposed in a Xenon-ArcWeather-Ometer under the following conditions:

[0605] Cam 180 cycle: 40 minutes light only; 20 minutes light and frontspray; 60 minutes light only; 60 minutes dark and rear spray condensate.

[0606] Lamp filters are: quartz inner/borosilicate S outer.

[0607] Irradiance: 0.55 watts per square meter.

[0608] 20° Gloss, Distinctness of Image, Hunter Color Space Values (L*,a*, b* and ΔE) are measured before exposure and after 3000 hours ofexposure.

[0609] The instant hindered amine compounds substituted on the N-atomwith an —O—E—OH moiety provide better stabilization efficacy to thepanels in respect to distinctness of image, gloss retention andresistance to color change than do the corresponding —NOR compoundslacking such a hydroxyl moiety.

EXAMPLE 113 ABS Molding Applications

[0610] Thermoplastic materials composed of mixtures of copolymersderived from the copolymerization of styrene monomer with acrylonitrileand the copolymerization of stryrene monomer with butadiene, generallyreferred to as ABS, are dry blended with the instant compounds and meltcompounded into pellets. Typical formulations contain the instantcompounds at levels from 0.05% to 2.0%, a metal stea ate such as calciumstearate at 0.05% to 0.5%, pigments from 0% to 5%, UV absorbers atlevels of 0.05% to 2.0%, phosphites at 0.0%-0.1%, phenolic antioxidantsat 0.0%-1.25%, N,N-dialkylhydroxylamine at 0.0%-0.1%, and optionallyother hindered amine stabilizers at levels of 0.0% to 2.0%.

[0611] The pelletized fully formulated resin is then processed into auseful article such as extrusion into sheet, film, profile and pipe;molded into bottles; injection molded into a molded article;thermoformed into molded articles; or rotational molded into hollowarticles.

[0612] The materials containing the instant compounds exhibit stabilityagainst deleterious effects of UV light and thermal exposure.

EXAMPLE 114

[0613] pK_(a) Values

[0614] In order to determine the pK_(a) values of water insolublematerials, organic references with known pK_(a) values in water aretitrated non-aqueously. A plot of the half neutralization potential(HNP) versus the known aqueous pK_(a) value of the reference material isestabled. The HNP of the test material is determined and extrapolated tofind the corresponding pK_(a) value of the test material. Such organicreference materials include 2,2,6,6tetramethyl-piperidine;4-hydroxy-2,2,6,6-tetramethylpiperidine;1-hydroxyethyl4hydroxy-2,2,6,6-tetra-methylpiperidine; triacetoneamineand N-methylaniline.

[0615] The reference materials, which are structurally at leastperipherally related to the instant test materials and are soluble inboth water and 1:1 acetonitrile:chloroform, are used to make acalibration plot in the non-aqueous titration (1:1acetonitrile:chloroform solvent and 0.1N perchioric acid/dioxanetitrant) system. Approximately 0.5 milliequivalents of test material isweighed into a titration beaker. Thirty mL of acetonitrile is added todissolve the sample. Prior to titration, 30 mL of chloroform is added.Titration is carried out and the HNP is determined. The electrolyte forthe reference electrode is 2-(aminomethylpyridine. The electrode isallowed to stand in the solvent system for two hours after filling withthe electrolyte to achieve equilibration. All samples are run induplicate. The pK_(a) values are seen in the table below. Sample* HPN(mv) Calculated pK_(a) I 523 3.9 II 436 4.9 III 513 3.8 IV — 4.6 V — 3.8VI — 4.8

[0616] As can be seen from each of the above pairs of related compoundswhere the individual compounds differ from the other only by whether the1-position of the piperidine ring is substituted by an —O—R group or byan —O—E—OH, the instant —C—E—OH compounds consisting have asignificantly lower pK_(a) value meaning that said instant compounds aredistinguished by consistently lower basicity than the prior art N—ORcompounds.

[0617] Inspection of the results given in Example 77 shows that thislower basicity and lower pK_(a) values can be translated into superiorperformance for the instant compounds compared to the closely relatedprior art N—OR compounds in preventing paint loss on paintablethermoplastic polyolefins (TPO).

EXAMPLE 115 Flame Retardancy

[0618] Fiber grade polypropylene, is dry blended with the test additivesand then melt compounded at 234° C. (450° F.) into pellets. Allformulations additionally contain melt processing stabilizer system. Thepelletized fully formulated resin is then spun at 246° C. (475° F.) intofiber using a Hills laboratory model fiber extruder. The spun tow of 41filaments is stretch at a ratio of 1:3.2 to give a final denier of615/41.

[0619] The fibers are then knitted into socks and on a Lawson-HemphillAnalysis Knitter. Ten a replicates of each sample are tested underNFPA701-1996 Vertical bum procedure. The time in seconds for the knittedsock to extinguish after the insult flame is removed is reported as“After Flame”. Efficacy as a flame retardant is demonstrated when lowAfter Flame times are observed relative to a blank sample containing noflame retardant. The burning time of the drips from the material and theweight loss are also recorded. The data demonstrates that the instantNOR HALS are effective as flame retardants. Weight loss Additive Afterflame (s) Drip Burn (s) (%) BLANK, no FR 32 >50 63 Compound of 0.5 12.536 Example 73, 1.0%

EXAMPLE 116 Flame Retardancy of Polypropylene Thick Sections

[0620] Molding grade polypropylene is dry blended with test additivesand then melt compounded into pellets. In addition to the instantcompound, halogenated flame retardants are included in the formulation.Typical formulations contain the instant compound and a flame retardantssuch as: tris(3bromo-2,2 bis (bromomethyl)propyl) phosphate (FMC PB370);bis(2,3-dibromopropyl ether) of bisphenol A (PE68);decabromodiphenyloxide (DBDPO); ethylene bis-tetrabromophthalimide(SATEX BT-93); ethylene bis-dibromonorbomanedicarboximide (SATEX BN451).Other formulations may contain Sb₂O₃ in addition to the brominated flameretardants. Other formulations may contain phosphorous based flameretardants such as ethylene diamine diphosphate (EDAP). The pelletizedfully formulated resin is then compression molded into test specimensusing a Wabash Compression Molder.

[0621] Test plaques are tested under UL-94 Vertical bum conditions. Aminimum of three replicates are tested. The average time in seconds forthe test sample to extinguish after a first and second insult flame isremoved is reported. Efficacy as a flame retardant is demonstrated whenlow Flame times are observed. The instant compounds enhance the flameretardancy of a halogenated or phosphate flame retardant tested alone.

EXAMPLE 117 Flame Retardancy in TPO Thick Sections

[0622] Molded test specimens were prepared by injection moldingthermoplastic olefin (TPO) pellets containing the instant compounds. TheTPO formulations may also contain pigments, a phenolic antioxidant,phosphite or hydroxylamine, a metal stearate, ultraviolet lightabsorbers (UVA) or a hindered amine stabilizers (HALS) or a mixture ofUV absorbers and hindered amine stabilizers.

[0623] In addition to the instant compound, halogenated flame retardantsare included in the formulation. Typical formulations contain theinstant compound and a flame retardants such as: tris(3-bromo2,2 bis(bromomethyl)propyl) phosphate (FMC PB370); bis(2,3-dibromopropyl ether)of bisphenol A (PE68); decabromodiphenyloxide (DBDPO); ethylenebis-tetrabromophthalimide (SATEX BT-93); ethylenebis-dibromonorbomanedi-carboximide (SATEX BN-451). Other formulationsmay contain Sb₂O₃ in addition to the brominated flame retardants. Otherformulations may contain phosphorous based flame retardants such asethylene diamine diphosphate (EDAP).

[0624] Test plaques are tested under UL-94 Vertical bum conditions. Aminimum of three replicates are tested. The average time in seconds forthe test sample to extinguish after a first and second insult flame isremoved is reported. The instant compounds enhance the flame retardancyof a halogenated or phosphate flame retardant tested alone.

EXAMPLE 118 Light Stability in Flame Retardant ABS Molding Applications

[0625] Molding grade ABS is dry blended with test additives and thenmelt compounded into pellets. In addition to the instant compounds,selected flame retardants are also included. The flame retardants aretris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, decabromodiphenyloxide, ethylene bis(tetrabromophthalimide) and ethylenebis(dibromonorbomanedicarboximide). The pelletized fully formulatedresin is then injection molded into test specimens using a BOY 50Mlaboratory model injection molder. Other formulations may containantimony trioxide (Sb₂O₃) in addition to the brominated flameretardants. Other formulation may contain phosphorus based flameretardants such as ethylenediamine diphophate (EDAP).

[0626] Test plaques are mounted in metal frame and exposed in an AtlasCi65 Xenon Arc Weather-O-meter with intermittent light dark cycles andwater spray following the ASTM G26 test procedure. Specimens are testedat periodic intervales for changes in tensile properties and for changesin color. The longer it takes for the loss in properties to occur andthe less the color change as measured by ΔE, the more effective is thestabilizer system.

[0627] The test samples containing the instant compounds exhibit goodretention of tensile properties and minimal color change during theaccelerated weathering.

EXAMPLE 119 Light Stability in Flame Retardant HIPS Molding Applications

[0628] Molding grade high impact polystyrene is dry blended with testadditives and then melt compounded into pellets. In addition to theinstant compounds, selected flame retardants are also included. Theflame retardants are tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate,decabromodiphen-4-yl oxide, ethylene bis(tetrabromophthalimide) andethylene bis(dibromo-norbomanedicarboximide). The pelletized fullyformulated resin is then injection molded into test specimens using aBOY 50M laboratory model injection molder. Other formulations maycontain antimony trioxide (Sb₂O₃) in addition to the brominated flameretardants. Other formulation may contain phosphorus based flameretardants such as ethylenediamine diphophate (EDAP).

[0629] Test plaques are mounted in metal frame and exposed in an AtlasCi65 Xenon Arc Weather-O-meter with intermittent light/dark cycles andwater spray following the ASTM G26 test procedure. Specimens are testedat periodic intervales for changes in tensile properties and for changesin color. The longer it takes for the loss in properties to occur andthe less the color change as measured by ΔE, the more effective is thestabilizer system.

[0630] The test samples containing the instant compounds exhibit goodretention of tensile properties and minimal color change during theaccelerated weathering.

EXAMPLE 120 Stabilization of High Solids Acid-catalyzed ThermosetAcrylic Resin Enamel

[0631] A high solids (50% by weight) thermoset acrylic resin enamel,catalyzed by 0.8% by weight of dodecylbenzenesulfonic acid, based on thefilm-forming resin is stabilized by the addition of various instantcompounds. The high solids thermoset acrylic resin enamel formulation(Acryloid AT 400 from Rohm and Haas) is based on hydroxyethylmethacrylate, methyl methacrylate, styrene, butyl acrylate and butylmethacrylate and a melamine curing agent.

[0632] Pieces of steel sheeting 4″×12″ (9.16 cm×30.48 cm), coated with aprimer based on polyester/epoxy resin, are then coated with aTiO₂-pigmented base coat based on a binder of 70% of monomers such ashydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate andacrylic acid with 30% of a melamine resin and an acid catalyst andfinally with a clear finishing enamel. The base coat is sprayed onto thesheet to a thickness of about 0.8 mil (0.0203 mm) and air dried forthree minutes. The clear finishing enamel is then sprayed onto the sheetto a thickness of about 2.0 mil. After 15 minutes air-drying, the coatedsheets are baked for 30 minutes at 121° C.

[0633] The stabilizers under test are added to the thermoset acrylicresin finishing enamel in a concentration of 1% by weight before theenamel is coated onto the base coat.

[0634] The coated sheets, after storage for three weeks in anair-conditioned room (23° C./50% relative humidity), are subjected toweathering for 2000 hours according to SAE J1920 in a Xenon arcWeather-Ometer. In this apparatus, samples are subjected to weatheringin repeated cycles of 180 minutes. The effectiveness of thestabilization is measured by the retention of 20° gloss afterweathering.

[0635] The sheets stabilized by the instant compounds exhibit goodretention of 20° gloss after weathering under extreme weatherconditions.

EXAMPLE 121

[0636] The samples prepared in Example 120 are also evaluated on thebasis of Knoop Hardness (ASTM D-147468) on baked and overbaked samples;on the distinction of image (DOI); on Hunter Associates Apparatus; on20° gloss (ASTM D-523-80); and on cracking based on visual observation.

[0637] The samples stabilized by the instant compounds exhibit a patternof greater retention of 20° gloss and DOI, and a longer absence ofsevere cracking after exposure.

EXAMPLE 122

[0638] The thermoset acrylic enamel of Example 120 is formulated toinclude 3% by weight of a benzotriazole UV absorber and 1.5% by weightof an instant hindered amine test compound. The enamel is coated over awhite base coat or over a silver metallic base coat. Baking is conductedat 121° C. normal bake or at 82° C. automotive low bake repairtemperature.

[0639] The coated panels are exposed in a Xenon arc exposure apparatusand 20° gloss and distinction of image (DOI) values are determined.

[0640] The samples stabilized by the instant compounds exhibit a patternof greater retention of 20° gloss and DOI.

EXAMPLE 123

[0641] Two thermoset acrylic enamles are formulated to include 3% byweight of a benzotriazole UV absorber and 1% by weight of an instanthindered amine test stabilizer.

[0642] The thermoset acrylic enamels are based on a binder of 70% ofmonomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butylacrylate and acrylic acid with 30% of a melamine resin and an acidcatalyst such as p-toluenesulfonic acid, dinonylnaphthalene-disulfonicacid, dodecylbenzenesulfonic acid or phenyl acid phosphate.

[0643] Pieces of steel sheeting 4″×12″ (9.16 cm×30.48 cm), coated with aprimer based on polyester/epoxy resin, are then coated with a base coatand finally with a clear finishing enamel. The base coat is sprayed ontothe sheet to a thickness of about 0.8 mil (0.0203 mm) and air dried forthree minutes. The clear finishing enamel is then sprayed onto the sheetto a thickness of about 2.0 mil. After 15 minutes air-drying, the coatedsheets are baked for 30 minutes at 121° C.

[0644] The coated panels are exposed in a Xenon arc exposure apparatusand 20° gloss and distinction of image (DOI) values are determined.

[0645] The samples stabilized by the instant compounds exhibit a patternof greater retention of 20° gloss and DOI.

EXAMPLE 124

[0646] A white polyester/melamine based oil-free alkyl coil coating isutilized in this example. The fully formulated paint is applied over aprimed steel sheet using a wire wound rod to give 0.6-0.8 mil dry film.The panels are baked for about 90 seconds at 220° C., removed from theoven and immediately quenched in water. The coated panels are exposed ina Xenon Arc Weather-Ometer, and in South Florida at an angle of 45° S tothe sun. 20° gloss values are determined.

[0647] The samples stabilized by the instant compounds exhibit a patternof greater retention of 20° gloss.

EXAMPLE 125

[0648] The thermoset acrylic enamel of Example 124 including 0.8%dodecylbenzenesulfonic acid is formulated to include varyingconcentrations of benzotriazole or s-triazine UV absorbers and theinstant hindered amine test compounds. The enamel is coated over asilver metallic base coat pursuant to the procedure of Example 124 andbaking is conducted for 30 minutes at 121° C. the normal backetemperature.

[0649] The coated panels are exposed in a Xenon arc Weather-Ometer andthe time to the 50% loss of 20° gloss is determined.

[0650] The samples stabilized by the instant compounds and a UV absorberexhibit an excellent retention of 20° gloss and a much longer time till50% loss in 20° gloss is observed.

EXAMPLE 126

[0651] A thermoset acrylic enamel based on a binder of 70% of monomerssuch as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylateand acrylic acid with 30% of a melamine resin and an acid catalyst suchas p-toluenesulfonic acid, dinonyinaphthalenedisulfonic acid ordodecylbenzenesulfonic acid is formulated. Commercially available 9.16cm×30.48 cm Uniprime panels are used as the substrate. The panels arecoated with a silver metallic base coat and then with a clear finishingenamel. The base coat is stabilized with 1% of a benzotriazole UVabsorber and 1% of an instant hindered amine test compound (based onsolid resin) and is sprayed onto the panel to a thickness of about0.6-0.8 mil and air dried for three minutes. The clear coat includingthe above-noted stabilizers is then sprayed to a thickness of 1.7-2.0mils and after 10 minutes of air drying, the coated panels are baked for30 minutes at 121° C. The coated panels are then exposed in a Xenon arcapparatus and the 20° gloss values are determined.

[0652] The samples stabilized by the instant compounds and a UV absorberexhibit excellent retention of 20° gloss.

EXAMPLE 127

[0653] A water-borne acrylic melamine enamel is formulated as seenbelow: Parts Resin Solids Synthacryl VSW 6483 30 (acrylic dispersionfrom Hoechst) Synthacryl VSW 6484 42 (50% acrylic resin in butyldiglycol, Hoechst) Maprenal MF 915 25 (70% melamine resin in isobutanol)Maprenal MF 927  3 (melamine resin) 100 

[0654] A water-based base coat/clear coat enamel is prepared by sprayapplying a 0.6-0.8 mil thick film of commercial silver metallicwaterborne base coat (from BASF) over an epoxy primed coil coatedaluminum panel. This material is baked at 80° C. for five minutes andthen clear coated with 1.6-1.8 mil of the waterborne enamel. The systemis baked at 80° C. for ten minutes and then at 140° C. for a further 30minutes. Prior to application of the clear coating, instant test andlight stabilizers dissolved in a minumum amount of butyl glycol acetateare added to the paint. The coated panels are exposed in a Xenon arcapparatus for 975 hours. The distinction of image (DOI) retention of thepanels is measured.

[0655] The samples stabilized by the instant compounds exhibit greaterretention of DOI values.

EXAMPLE 128 Stabilization of Tung Oil Phenolic Varnish

[0656] Pieces of 1.27 cm×20.32 cm×30.48 cm western red cedar panelshaving a fine radial cut are used to test a commercially available tungoil phenolic varish (supplied by McCloskey). One half of each panel iscoated with two coats of unstabilized varnish. An equal amount ofvarnish containing 5% by weight (based on resin solids) of teststabilizers is applied to the other half of the panel in two coats.After storage for two weeks at ambient temperature, the wood panels areexposed outdoors at an angle of 45° S for a period of eight months. The60° gloss of each half of the panel is measured at the top, middle andbottom portion of the panel and averaged according to ASTM D 523. Due tothe lack of homogeneity of wood substrates, the gloss retention of thesame varnish tends to differ slightly from panel to panel. Thus, theapplication of an unstabilized control varnish to every panel allows fora more meaningful measurement of the improvement in gloss due to thepresence of the instant test compound.

[0657] The panels stabilized by the instant compounds show excellentgloss retention after long exposure.

EXAMPLE 129 Stabilization of an Aromatic Urethane Varnish

[0658] A sample of commercial aromatic urethane varnish(Flecto-Varathane #90) is tested by the same method described in Example128. After outdoor exposure at an angle of 45° S for a period of fivemonths, the 60° gloss retention values of unstabilized and stabilizedportions of the panels are determined.

[0659] The panels stabilized by the instant compounds show excellentgloss retention.

EXAMPLE 130 Stabilization of a White Two-Component Polyester UrethaneGloss Enamel

[0660] A white polyester is formulated as shown below: Parts Component IDesmophen 670-90 (polyester glycol, Mobay) 132.4 Titanium Dioxide 198.6Cellosolve Acetate 98.9 Sand Mill Desmophen 670-90 94.98 Flow Aid 0.28Tertiary Amine 0.015 Cellosolve Acetate 332.6 Component II DesmodurN-100 (polyisocyanate, Mobay) 93.9 Cellosolve Acetate 58.7

[0661] This material is spray applied at a dry film thickness of 1.5-2.0mil onto Bonderite 40 cold rolled steel panels that have been previouslyprimed with a commerical epoxy polyamide maintenance primer(Sherwin-Williams Tile Clad II). Prior to application, the instant testcompounds are added to the paint. After ambient storage for two weeks,three panels of each formulation are exposed outdoors at an angle of 45°S for a period of nine months. Thereafter, 20° gloss retention isdetermined by ASTM D 52380 at the top, middle and bottom portions ofeach panel. Thus, the average values for nine gloss retentionmeasurements for each triplicate set of panels are obtained.

[0662] The panels stabilized by the instant compounds show excellentgloss retention.

EXAMPLE 131 Stabilization of Acrylic Alkyd Refinish Enamel

[0663] A commercially available acrylic alkyd enamel pigments withnon-leafing aluminum pigment and tinted a light blue is stabilized witha benzotriazole UV absorber and an instant hindered amine test compoundand is then spray applied onto Bonderite 40 panels primed with an alkydprimer. After the coating is allowed to cure at room temperature for 14days, the panels are exposed outdoors at an angle of 45° S for a periodof eight months. The 20° gloss of the exposed panels is measured.

[0664] The panels stabilized by the instant compounds show excellentgloss retention.

EXAMPLE 132 Stabilization of a Medium Oil Alkyd Enamel

[0665] A medium oil alkyd enamel pigmented with a non-leafing aluminumpigment and tinted light blue is stabilized with a benzotriazole UVabsorber and an instant hindered amine test compound and is then sprayedapplied onto cold rolled steel panels primed with an epoxy primer. Afterthe coating is allowed to cure at room temperature for two weeks, thepanels are exposed for accelerated weathering in a Xenon ArcWeather-Ometer for 840 hours. The 20° gloss values of the panels aredetermined before and after exposure.

[0666] The panels stabilized by the instant compounds show excellentgloss retention.

EXAMPLE 133 Electrocoat Composition

[0667] A typical E-coat composition is prepared by adding thediglyicidyl ether of bisphenol A, polyethylene oxide diol, bisphenol Aand xylene to a flask and heating to 135° C. The catalystdimethylbenzylamine in xylene is added and the temperature maintained at143° C. for two hours. The weight per epoxy (WPE) is measured and apreviously prepared crosslinker composed of 2,4-toluenediisocyanate,trimethylolpropane blocked with an alcohol is then added and temperaturereduced to 100° C. The remaining epoxy groups are then capped with twodifferent secondary amines, namely diketimine of diethylenetriamine andmethylethanolamine, in phenyl cellosolve. The temperature is maintainedfor one hour at 110° C. and the crosslinker hexamethylenediisocyanateblocked with an alcohol is added. The temperature is maintained near100° C. for 30 minutes and the resin mixture is added to deionizedwater, surfactant and lactic acid to give a resin emulsion.

[0668] To this resin emulsion is added the instant hindered aminecompound, additional epoxy resin, carbon black, dibutyltin oxidecatalyst, titanium dioxide, lead silicate, water and UV absorber. Afterdispersion using a sand mill to achieve proper fineness, the mixture isincorporated into an electrocoat bath with water for electrocoating ontoa metal substrate.

[0669] The steel coating electrocoated with the above E-coat resincomposition to a thickness of 23-30 μm and cured for 20 minutes at atemperature of 176-201° C. A pigmented resin layer is coated thereoverat a thickness of 20-51 μm using an acrylic coating composition in anorganic solver, pigments and a UV absorber. The coated panels are thenbaked at 121-129° C. to cure the pigmented layer.

[0670] The panels are then exposed outdoors for four months. The panelscontaining the instant hindered amine compound, particularly when usedwith a UV absorber, provided excellent resistance to delamination of theE-coat layer from the metal substrate.

EXAMPLE 134 Abrasion-Resistant Coating Compositions

[0671] A solution in isopropanol of 50% (by weight) of 1,6-hexanediol,10% 3-methacryloyloxy-propyltrimethoxysilane and 40% colodial silica (inform of a 34% aqueous dispersion) is vacuum stripped to remove volatilesand combined with an instant hindered amine compound, a benzotriazole UVabsorber and 2,4,6-trimethylbenzoyldiphenylphosphine photoinitiator.These compositions show no gelation on storage.

[0672] The compositions above are applied by roller coating to a 15 milfilm of bisphenol A polycarbonate and the coated films are passed undera mercury lamp at 43° C. at a line speed of 610 cm/min. The compositionsare cured to a colorless and optically clear coatings over thepolycarbonate substrate.

[0673] The coatings as measured by the Taber Abrasion Test (ASTM D1044)are abrasion resistant.

[0674] The test specimens are also subjected to accelerated aging testsusing an Atlas Ci35A Xenon Arc Weather-Ometer. The results show that thecoatings containing the instant hindered amine compound exhibitexcellent resistance to yellowness and haze formation.

EXAMPLE 135 Coating over Polycarbonate

[0675] A two-component polyester urethane coating is stabilized by theaddition of an instant hindered amine compound. The high-solidspolyester polyol (Desmophen 670-80, Bayer) is crosslinked with anisocyanate based resin (Desmodue N-3390, Bayer). The coating iscatalyzed with 0.015% by weight of dibutyltin dilaurate catalyst.

[0676] Plaques of polycarbonate-based plastic substrate (Xenoy) 4″×6″are coated with the formulated clear coat at a thickness ofapproximately 1.5 mils. The coating is spray applied to the substrateand then baked at 82° C. for 20 minutes.

[0677] After storage for one week at room temperature, each plaque iscut into 2″×3″ strips with five replicates being made for eachformulation. Each strip is placed into a 8-oz jar along with 2 mL ofdistilled water and sealed. All samples are placed in an over at 54° C.A crosshatch adhesion test is performed once a week on at least two ofthe replicate samples until the sample failed (5% adhesion loss) oruntil 40 days elapses.

[0678] The samples containing the instant hindered amine compoundsexhibit excellent resistance to delamination.

What is claimed is:
 1. A compound having 1-alkoxy substituted hinderedamine derivatives where the alkoxy moiety is substituted by one to threehydroxy groups as described in formulas (1) to (15); or to novelcompounds having 1-alkoxy bridged hindered amine derivatives where thealkoxy moiety, substituted by one to three hydroxy groups, is shared bytwo hindered amine molecules as described in formulas (16) to (28); orto oligomeric or polymeric hindered amine molecules made from thereaction of dialkyl esters or isocyanates with hydroxy substitutedN-alkoxy derivatives of 4-hydroxy-2,2,6,6-tetraalkylpiperidine asdescribed in formula (29); or to simple diester or urethane derivativesof hydroxy substituted N-alkoxy derivatives of4hydroxy-2,2,6,6-tetramethylpiperidine as described in formula (30)

wherein G₁ and G₂ are independently alkyl of 1 to 4 carbon atoms, or G₁and G₂ together are pentamethylene; preferably G₁ and G₂ are eachmethyl; E is a straight or branched chain alkylene of 1 to 18 carbonatoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18carbon atoms, a straight or branched chain alkylene of 1 to 4 carbonatoms substituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms; b is 1, 2 or 3 with the proviso that bcannot exceed the number of carbon atoms in E or L, and when b is 2 or3, each hydroxyl group is attached to a different carbon atoms of E orL; the two hindered amine groups are generally, but not always, attachedto two different carbon atoms of L; in each of the formulas (1) to (15)m is 0 or 1; R₁ is hydrogen, hydroxyl or hydroxymethyl; R₂ is hydrogen,alkyl of 1 to 12 carbon atoms or alkenyl of 2 to 12 carbon atoms; n is 1to 4; when n is 1, R₃ is alkyl of 1 to 18 carbon atoms,alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl of 2 to18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms which alkylis interrupted by oxygen, an acyl radical of an aliphatic or unsaturatedaliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms,an acyl radical of a cycloaliphatic carboxylic or carbamic acidcontaining 7 to 12 carbon atoms, or acyl radical of an aromatic acidcontaining 7 to 15 carbon atoms; when n is 2, R₃ is alkylene of 2 to 18carbon atoms, a divalent acyl radical of an aliphatic or unsaturatedaliphatic dicarboxylic or dicarbamic acid containing 2 to 18 carbonatoms, a divalent acyl radical of a cycloaliphatic dicarboxylic ordicarbamic acid containing 7 to 12 carbon atoms, or a divalent acylradical of an aromatic dicarboxylic acid containing 8 to 15 carbonatoms; when n is 3, R₃ is a trivalent acyl radical of an aliphatic orunsaturated aliphatic tricarboxylic acid containing 6 to 18 carbonatoms, or a trivalent acyl radical of an aromatic tricarboxylic acidcontaining 9 to 15 carbon atoms; when n is 4, R₃ is a tetravalent acylradical of an aliphatic or unsaturated aliphatic tetracarboxylic acid,especially 1,2,3,4-butanetetracarboxylic acid,1,2,3,4-but-2-enetetracarboxylic acid, 1,2,3,5-pentanetetracarboxylicacid and 1,2,4,5-pentanetetracarboxylic acid, or R₃ is a tetravalentacyl radical of an aromatic tetracarboxylic acid containing 10 to 18carbon atoms; p is 1 to 3, R₄ is hydrogen, alkyl of 1 to 18 carbon atomsor acyl of 2 to 6 carbon atoms; when p is 1, R₅ is hydrogen, alkyl of 1to 18 carbon atoms, an acyl radical of an aliphatic or unsaturatedaliphatic carboxylic or carbamic acid containing 2 to 18 carbon atoms,an acyl radical of a cycloaliphatic carboxylic or carbamic acidcontaining 7 to 12 carbon atoms, an acyl radical of an aromaticcarboxylic acid containing 7 to 15 carbon atoms, or R₄ and R₅ togetherare —(CH₂)₅CO—, phthaloyl or a divalent acyl radical of maleic acid;when p is 2, R₅ is alkylene of 2 to 12 carbon atoms, a divalent acylradical of an aliphatic or unsaturated aliphatic dicarboxylic ordicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl radicalof a cycloaliphatic dicarboxylic or dicarbamic acid containing 7 to 12carbon atoms, or a divalent acyl radical of an aromatic dicarboxylicacid containing 8 to 15 carbon atoms; when p is 3, R₅ is a trivalentacylradical-of-analiphatic or unsaturated aliphatic tricarboxylic acidcontaining 6 to 18 carbon atoms, or a trivalent acyl radical of anaromatic tricarboxylic acid containing 9 to 15 carbon atoms; when n is1, R₆ is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbonatoms, —NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of 2 to 36 carbonatoms, when n is 2, R₆ is alkylenedioxy of 2 to 18 carbon atoms,alkenylenedioxy of 2 to 18 carbon atoms, —NH-alkylene-NH— of 2 to 18carbon atoms or —N(alkyl)-alkylene-N(alkyl)— of 2 to 18 carbon atoms, orR₆ is 4-methyl-1,3-phenylenediamino, when n is 3, R₆ is a trivalentalkoxy radical of a saturated or unsaturated aliphatic triol containing3 to 18 carbon atoms, when n is 4, R₆ is a tetravalent alkoxy radical ofa saturated or unsaturated aliphatic tetraol containing 4 to 18 carbonatoms, R₇ and R₈ are independently chlorine, alkoxy of 1 to 18 carbonatoms, —O—T₁, amino substituted by 2-hydroxyethyl, —NH(alkyl) of 1 to 18carbon atoms, —N(alkyl)T₁ with alkyl of 1 to 18 carbon atoms, or—N(alkyl)₂ of 2 to 36 carbon atoms, R₉ is a divalent oxygen atom, or R₉is a divalent nitrogen atom substituted by either hydrogen, alkyl of 1to 12 carbon atoms or T₁

R₁₀ is hydrogen or methyl, q is 2 to 8, R₁₁ and R₁₂ are independenulyhydrogen or the group T₂

R₁₃ is hydrogen, phenyl, straight or branched alkyl of 1 to 12 carbonatoms, alkoxy of 1 to 12 carbon atoms, straight or branched alkyl of 1to 4 carbon atoms substituted by phenyl, cycloalkyl of 5 to 8 carbonatoms, cycloalkenyl of 5 to 8 carbon atoms, alkenyl of 2 to 12 carbonatoms, glycidyl, allyloxy, straight or branched hydroxyalkyl of 1 to 4carbon atoms, or silyl or silyloxy substituted three times independentlyby hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by alkoxy of1 to 4 carbon atoms; R₁₄ is hydrogen or silyl substituted three timesindependently by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms orby alkoxy of 1 to 4 carbon atoms; d is 0 or 1; h is 0to 4; k is 0 to 5;x is 3 to 6; y is 1to 10; z is an integer such that the compound has amolecular weight of 1 000 to 4000 amu, R₁₅ is morpholino, piperidino,1-piperizinyl, alkylamino of 1 to 8 carbon atoms, especially branchedalkylamino of 3 to 8 carbon atoms such as tert-octylamino, —N(alkyl)T₁with alkyl of 1 to 8 carbon atoms substituted by T₁ or —N(alkyl)₂ of 2to 16 carbon atoms, R₁₆ is hydrogen, acyl of 2 to 4 carbon atoms,carbamoyl substituted by alkyl of 1 to 4 carbon atoms, s-triazinylsubstituted once by chlorine and once by R₁₅, or s-triazinyl substitutedtwice by R₁₅ with the condition that the two R₁₅ substituents may bedifferent; R₁₇ is chlorine, amino substituted by alkyl of 1 to 8 carbonatoms or by T₁, —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms,—N(alkyl)₂ of 2 to 16 carbon atoms, or the group T₃

R₁₈ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl substituted byalkyl of 1 to 4 carbon atoms, s-triazinyl substituted twice by—N(alkyl)₂ of 2 to 16 carbon atoms or s-triazinyl substituted twice by—N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms; L is straight or branchedchain alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8 carbonatoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of 3 to 18carbon atoms, a straight or branched chain alkylene of 1 to 4 carbonatoms substituted by phenyl or by phenyl substituted by one or two alkylof 1 to 4 carbon atoms, in formulas (16) to (28), R₁, R₂, R₇, R₈, R₉,R₁₀, R₁₃, R₁₄, d,h, k, m, q, and T₁ have the same meanings as informulas (1) to (15); R₁₉ is hydrogen, alkyl of 1 to 18 carbon atoms,alkenyl of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl,2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atomswhich alkyl is interrupted by oxygen, an acyl radical of an aliphatic orunsaturated aliphatic carboxylic or carbamic acid containing 2 to 18carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamicacid containing 7 to 12 carbon atoms, or acyl radical of an aromaticacid containing 7 to 15 carbon atoms; R₂₀ is alkylene of 2 to 18 carbonatoms, a divalent acyl radical of an aliphatic or unsaturated aliphaticdicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, adivalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamicacid containing 7 to 12 carbon atoms, or a divalent acyl radical of anaromatic dicarboxylic acid containing 8 to 15 carbon atoms; R₂₁ ishydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6 carbon atoms;R₂₂ is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical of analiphatic or unsaturated aliphatic carboxylic or carbamic acidcontaining 2 to 18 carbon atoms, an acyl radical of acycloaliphatic-carboxylicorcarbamic acidcontaining 7 to 12 carbon atoms,an acyl radical of an aromatic carboxylic acid containing 7 to 15 carbonatoms, or R₄ and R₅ together are —(CH₂)₅CO—, phthaloyl or a divalentacyl radical of maleic acid; R₂₃ is hydrogen, alkyl of 1 to 4 carbonatoms or acyl of 2 to 6 carbon atoms; R₂₄ is alkylene of 2 to 18 carbonatoms, a divalent acyl radical of an aliphatic or unsaturated aliphaticdicarboxylic or dicarbamic acid containing 2 to 18 carbon atoms, adivalent acyl radical of a cycloaliphatic dicarboxylic or dicarbamicacid containing 7 to 12 carbon atoms, or a divalent acyl radical of anaromatic dicarboxylic acid containing 8 to 15 carbon atoms; R₂₅ isalkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18 carbon atoms,—NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of 2 to 36 carbon atoms,R₂₆ is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of 2 to 18carbon atoms, —NH-alkylene-NH— of 2 to 18 carbon atoms or—N(alkyl)-alkylene-N(alkyl)— of 3 to 18 carbon atoms, in formulas (29)and (30), G is a carbon centered diradical derived from a primary,secondary or tertiary alcohol G—OH, where z is as defined above, and Gis straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene of 5 to 8 carbonatoms, alkenylene of 3 to 18 carbon atoms, a straight or branched chainalkylene of 1 to 4 carbon atoms substituted by phenyl or by phenylsubstituted by one or two alkyl of 1 to 4 carbon atoms, with the provisothat in formula (29) successive hindered amine moieties can be orientedin either a head to head or head to tail fashion; T₄ is hydrogen or

R₂₇ is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene or cycloalkenylene of 5 to 8 carbon atoms, phenylene or—NH-alkylene-NH— of 2 to 18 carbon atoms including5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane and —NH-xylyIene-NH—;R₂₈ is alkyl of 1 to 4 carbon atoms;

R₂₉ is a straight or branched chain alkyl or —NH-alkyl of 1 to 18 carbonatoms or —NH— cycloalkyl of 5 to 8 carbon atoms; and with the furtherproviso that in formulas (1) and (2), when b is 1, E is not methyl,ethyl, 2-propyl or 2-methyl-2-propyl.
 2. A compound according to claim 1wherein G₁ and G₂ are each methyl.
 3. A compound according to claim 1where in formulas (1) to (28), b is 1 or 2, when b is 1, E—OH and L—OHare respectively a carbon-centered radical or diradical formedpreferably from 2-methyl-2-propanol, 2-propanol,2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol,1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol,1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, cyclohexanol,cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1-ethanol;most preferably E—OH and L—OH are formed from 2-methyl2-propanol orcyclohexanol, when b is 2, E—OH and L—OH are respectively acarbon-centered radical or diradical formed preferably from1,2-ethanediol, 1,2-propanedial, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4cyclohexanediol; when bis 3, E—OH and L—OH are respectively a carbon-centered radical ordiradical formed from glycerol, 1,1,1-tris(hydroxymethyl)methane,2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or1,2,6-hexanetriol; in formulas (29) and (30), —G—O is formed fromethanol, phenethyl alcohol, cyclohexanol or 2-methyl-2-propanol(=tert-butyl alcohol); in formula (3), m is 0, R₁ is hydrogen orhydroxymethyl, and R₂ is hydrogen; or m is 1, R₁ is hydroxy orhydroxymethyl, and R₂ is hydrogen, methyl or ethyl; in formula (5), R₂is hydrogen or dodecyl; in formula (6), n is 1 or 2, and when n is 1, R₃is allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl,tetradecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl,methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R₃is succinyl, glutaryl, adipoyl, sebacoyl, 1,6hexanedicarbamoyl or cis-or trans-5-carbamoyl-1-(carbamoyl-methyl)-1,3,3-trimethylcydohexane; informula (7), p is 1 or 2, and when p is 1, R₄ is hydrogen and R₅ isbutyl; or R₄ and R₅ together are the divalent acyl radical of maleicacid; or when p is 2, R₄ is hydrogen or acetyl, and 5 is 1,6-hexanediyl;in formula (8), n is 1 or 2, and when n is 1, R₆ is ethoxy,6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; or when n is2, R₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino,hexamethylenediamino or 4-methyl-1,3-phenylenediamino; in formula (9),R₇ and R₈ are independently chlorine, octylamino, tert-octylamino oramino substituted by T₁ and ethyl, butyl or dodecyl; and R₉ is adivalent nitrogen atom substituted by ethyl, butyl or dodecyl; informula (10), q is 2, 4 or 6, R₇ is chlorine, octylamino, octadecylaminoor amino substituted by T₁ and ethyl, butyl or dodecyl; and R₁₀ ishydrogen; in formula (11), n is 3, p is 2, R₂is ethyl, butyl or dodecyl;and one of R₁₁ or R₁₂is T₂, and the other is hydrogen; in formula (12),k is 3, R₉ is a divalent oxygen atom or is a divalent nitrogen atomsubstituted by ethyl, butyl or dodecyl, R₁₃is hydrogen or methyl, andwhen d is 0, x is 5 or 6, and when d is 1, x is 3 or 4; in formula (13),d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, R₉ is a divalent oxygenatom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl,R₁₃is hydrogen, methyl, ethyl, methoxy or ethoxy, and R₁₄is hydrogen ortrimethylsilyl; in formula (14), R₉ is a divalent oxygen atom, R₁₀ ishydrogen or methyl, m is 0 and z is an integer such that the molecularweight of the compound is 1500-3000 amu; in formula (15) q is 6, y is1-7, R₁₅ is tert-octylamino, morpholino, amino substituted by T₁ andbutyl, which may also be designated as T₁-butylamino, R₁₆ is hydrogen,acetyl, ethyl-carbamoyl, 2,4-bis(dibutylamino)-s-triazinyl,2,4-bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice byT₁-butylamino or s-triazinyl substituted once by diethylamino ordibutyl-amino and once by T₁-butylamino, R₁₇ is dibutylamino,diethylamino, T₁-butylamino or R₁₇ is T₃ where R₁₈ is acetyl orethylcarbamoyl; in formula (17), m is 0, R₁ is hydrogen orhydroxymethyl, and R₂ is hydrogen; or m is 1, R₁ is hydroxy orhydroxymethyl, and R₂ is hydrogen or methyl; in formula (19), R₂ ishydrogen or dodecyl; in formula (20), R₁₉ is hydrogen, allyl, acryloyl,methacryloyl, octadecanoyl or hexadecanoyl; in formula (21), R₂₀ issuccinyl, glutaryl, adipoyl, sebacoyl, 1,6hexanedicarbamoyl, or cis- ortrans-5-carbamoyl-1-(carbamoylmethyl)-1,3,3-trimethylcyclohexane; informula (22), R₂₁ is hydrogen and R₂₂ is hydrogen or butyl; or R₂₁ andR₂₂ together are the divalent acyl radical of maleic acid; in formula(23), R₂₃ is hydrogen or acetyl, and R₂₄ is ethylene or hexamethylene;in formula (24), R₂₅ is ethoxy, 6-methyl-1-heptyloxy, ethylamino,butylamino or octyl-amino; in formula (25), R₂₆ is 1,2-ethanedioxy,1-4-butanedioxy, ethylenediamino or hexamethylenediamino; in formula(26), R₇ and R₈ are independently chlorine, octylamino, tert-octylamino,octadecylamino, T₁-ethylamino, T₁-butylamino or T₁-dodecylamino, and R₉is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl; informula (27), q is 2, 4 or 6, R₇ is chlorine, octylamino,octadecylamino, T₁-ethylamino, T₁-butylamino or T₁-dodecylamino, and R₁₀is hydrogen; in formula (28), d is 0 or 1, h is 0-2, k is 0 or 3, R₉ isa divalent oxygen atom or a divalent nitrogen atom substituted by ethyl,butyl or dodecyl, R₁₃ is hydrogen, methyl, ethyl, methoxy or ethoxy, andR₁₄ is hydrogen or trimethylsilyl; in formula (29), R₂₇ is ethylene,trimethylene, tetramethylene, octamethylene, 1,6-diaminohexane or5-amino-1-aminomethyl1,3,3-trimethylcyclohexane; z is an integer suchthat the molecular weight of the compound is 1500-3000 amu, R₂₈ ismethyl or ethyl, and G is ethylene, 1,2-cyclohexanediyl,1,3-cyclohexanediyl, 1,4-cyclohexanediyl, —CH(C₆H₅)CH₂— or —CH₂C(CH₃)2—;and in formula (30), R₂₉ is pentadecyl, heptadecyl, butylamino orcyclohexylamino.
 4. A compound according to claim 1 where in formula(6), when n is 1, R₃ is acryloyl, methacrloyl, glycidyl, octadecanoyl,hexadecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl,methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or when n is 2, R₃is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl or cis-or trans-5carbamoyl-1-(carbamoylmethyl)-1,3,3-trimethylcyclohexane; informula (7), p is 1 or 2, and when p is 1, R₄ is hydrogen and R₅ ishydrogen or butyl; or when p is 2, R₄ is hydrogen, and R₅ is1,6-hexanediyl; in formula (9), R₇ is chlorine, octylamino orT₁-butylamino, R₈ is chlorine or T₁-butylamino, and R₉ is a divalentnitrogen atom substituted by butyl; in formula (10), q is 6, R₇ isT₁-butylamino; and R₁₀ is hydrogen; in formula (11), n is 3, p is 2, andone of R₁₁ or R₁₂ is T₂, and the other is hydrogen; in formula (12), kis 3, R₉ is a divalent oxygen atom, R₁₃ is hydrogen or methyl, and d is0, x is 5 or 6, and when d is 1, x is 3 or 4; in formula (13), d is 0 or1, h is 0-2, k is 0 or 3, y is 1-8, R₉ is a divalent oxygen atom, R₁₃ ishydrogen, methyl, ethyl, methoxy or ethoxy, and R₁₄ is hydrogen ortrimethylsilyl; in formula (15) q is 6, y is 1-7, R₁₅ is T₁-butylamino,R₁₆ is hydrogen, acetyl, ethyl-carbamoyl,2,4-bis(dibutylamino)-s-triazinyl, 2,4-bis(diethylamino)-s-triazinyl,s-triazinyl substituted twice by T₁-butylamino or s-triazinylsubstituted once by diethylamino or dibutylamino and once byT₁-butylamino, R₁₇ is dibutylamino, diethylamino, T₁-butylamino or R₁₇is T₃ where R₁₈ is acetyl or ethylcarbamoyl; in formula (20), R₁₉ ishydrogen, octadecanoyl or hexadecanoyl; in formula (22), R₂₁ is hydrogenand R₂₂ is hydrogen or butyl; in formula (23), R₂₃ is hydrogen, and R₂₄is hexamethylene; in formula (26), R₇ is chlorine, octylamino orT₁-butylamino, R₈ is chlorine or T₁-butylamino, and R₉ is a divalentnitrogen atom substituted by butyl; in formula (27), q is 6, R₇ isT₁-butylamino, and R₉ is a divalent nitrogen atom substituted by butyl;in formula (29), R₂₇ is ethylene, trimethylene, tetramethylene oroctamethylene, z is an integer such that the molecular weight of thecompound is 1500 to 2000 amu, and R₂₈ is methyl; and in formula (30),R₂₉ is pentadecyl or heptadecyl.
 5. A compound according to claim 1wherein the compounds of formulas (1) to (30) where E—OH, L—OH and —G—O—are formed from 2-methyl-2-propanol (=tert-butyl alcohol).
 6. A compoundaccording to claim 1 where in formula (6) when n is 1, R₃ is acryloyl,methacryloyl, glycidyl, octadecanoyl, hexadecanoyl,methoxycarbonylpropionyl or methoxycarbonylbutyryl, and when n is 2, R₃is succinyl, glutaryl, adipoyl or sebacoyl; in formula (7) where R₄ ishydrogen, and when p is 1, R₅ is hydrogen or butyl, or when p is 2, R₅is hexamethylene; in formula (9) where R₇ is chlorine, octylamino orT₁-butylamino, R₈ is T₁-butylamino, and R₉ is a divalent nitrogen atomsubsbtuted by butyl; in formula (10) where q is 6, R₇ is T₁-butylaminoand R₁₀ is hydrogen; in formula (11) where n is 3, p is 2, one of R₁₁ orR₁₂ is T₂ and the other is hydrogen; in formula (12) where d is 1, k is3, x is 3 or 4, R₉ is divalent oxygen atom, and R₁₃ is methyl; informula (13)where k is 3,y is 4-8, R₉ is a divalent oxygen atom, R₁₃ ishydrogen or methyl, d and h are 0, R₁₄ is hydrogen, or d is 1 and h is0, and R₁₄ is trimethylsilyl; in formula (14) where m is 0, R₉ is adivalent oxygen atom, R₁₀ is hydrogen or methyl, and z is an integersuch that the molecular weight of the compound is 1500-3000 amu; informula (15) where q is 6, y is 1-7, R₁₅ is T₁-butylamino, R₁₆ ishydrogen, acetyl, ethylcarbamoyl, 2,4-bis(dibutylamino)-s-triazinyl,2,4-bis(diethylamino)-s-triazinyl, s-triazinyl substituted twice byT₁-butylamino or s-triazinyl substituted once by diethylamino ordibutyl-amino and once by T₁-butylamino, R₁₇ is dibutylamino,diethylamino, or T₃ where R₁₈ is acetyl or ethylcarbamoyl; in formula(20) where R₁₉ is hydrogen, octadecanoyl or hexadecanoyl; and in formula(21) where R₂₀ is succinyl, glutaryl, adipoyl or sebacoyl; and informula (30) where R₂₉ is heptadecyl.
 7. A compound according to claim 1wherein the compound of formula (1) to formula (30) is prepared from2-methyl-2-propanol (=tert-butyl alcohol) or cyclohexanol.
 8. A compoundaccording to claim 1 which is (a)bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)]sebacate;(b) a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarate andbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;(c)1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperdine;(d)bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate;(e)bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpipeidin-4-yl]glutarate;(f)bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpipedin-4-yl]succinate;(g) a mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]glutarateandbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]succinate;(h)1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane;(i)1-(2-hydroxy-2-methylpropoxy)-4-[9-(methoxy-carbonyl)nonanoyloxy]-2,2,6,6-tetramethylpiperidine;(j)1-(2-hydroxy-2-methylpropoxy)-4-[5-(methoxy-carbonyl)pentanoyloxy]-2,2,6,6-tetramethylpiperidine;(k)1-(2-hydroxy-2-methylpropoxy)-4-[3-(methoxy-carbonyl)propion-4-yloxy]-2,2,6,6-tetramethylpiperidine;(l)1-(2-hydroxy-2-methylpropoxy)-4-[4-(methoxy-carbonyl)butyryloxy]-2,2,8,6-tetramethylpiperidine;(m) condensation product of4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinewith hexamethylene diisocyanate and terminated with methoxy; (n)condensation product of4-hydroxy-1-(2-hydroxy-ethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy; (o) condensationproduct of4-hydroxy-1-(2-hydroxy-1-phenethoxy)-2,2,6,6-tetramethylpiperidine withhexamethylene diisocyanate and terminated with methoxy; (p)1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperdine;or (q)1-(4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy)-2-hexadecanoyloxy-2-methylpropane.9. A composition which comprises (a) an organic polymer subject to theadverse effects of heat, oxygen and light, and (b) an effectivestabilizing amount of one or more compounds selected from the compoundsof formula (1) to formula (30) as described according to claim
 1. 10. Acomposition according to claim 9 wherein component (a) is athermoplastic polyolefin, polyester, polyester urethane, polyetherurethane or a water-borne coating.
 11. A composition according to claim9 wherein component (a) is selected from the group consisting ofpolypropylene, thermoplastic polyolefin, low density polyethylene,medium density polyethylene, high density polyethylene, linear lowdensity polyethylene, poly(butene-1), ethylene/vinyl acetate copolymer,ethylene/propylene copolymer, copolymers of ethylene or propylene withother alpha-olefins, copolymers of acrylonitrile-butadiene-styrene(ABS), copolymers of acrylonitrile and styrene that are impact modifiedwith ethylene-propylene rubber or ethylene/propylene/alpha-olefin rubberor butyl acrylate rubber, blends of ABS and polycarbonate, blends of ABSand poly(vinyl chloride) (PVC), poly(vinyl chloride), copolymers ofstyrene and butadiene (HIPS), copolymers of styrene and butadiene thatalso contain ethylene-propylene rubber orethylene/propylene/alpha-olefin rubber or butyl acrylate rubber,thermoplastic elastomers and thermoplastic vulcanizates.
 12. Acomposition according to claim 9 wherein component (a) is a polyester orpolyether urethane or water-borne coating.
 13. A composition accordingto claim 9 which additionally contains an effective stabilizing amountof at least one coadditive stabilizer selected from the group consistingof the phenolic antioxidants, metal stearates, metal oxides,organophosphorus compounds, furanone antioxidants, hydroxylamines, UVabsorbers, non-NOR hindered amines, NOR hindered amines and mixturesthereof.
 14. A composition according to claim 9 which additionallycontains a filler.
 15. A composition according to claim 14 wherein thefiller is calcium carbonate, clay, talc, mica or glass.
 16. Acomposition according to claim 9 wherein component (a) is anagricultural film which is exposed to pesticides.
 17. A compositionaccording to claim 9 wherein component (a) is an agricultural filmexposed to pesticides, and component (b) additionally contains a metalstearate and zinc oxide.
 18. A composition according to claim 9 whereincomponent (a) is a polyolefin film, fiber or thick section, ABS, highimpact polystyrene (HIPS), thermoplastic polyolefin, thermoplasticelastomer or thermoplastic vulcanizate which additionally contains ahalogenated flame retardant.
 19. A composition according to claim 18wherein the flame retardant istris[3bromo-2,2-bis(bromomethyl)propyl]phosphate, decabromodiphenyloxide, ethylene bis(tetrabromophthalimide) or ethylenebis(dibromonorbomanedicarboximide).
 20. A composition according to claim18 wherein component (a) is polypropylene fiber.
 21. A compositionaccording to claim 9 wherein component (a) is polypropylene,polyethylene, thermoplastic polyolefin (TPO), ABS or high impactpolystyrene (HIPS), and component (b) is an effective synergisticmixture of (i) a compound of formula (1) to (30) according to claim 9;and (ii) a flame retardant selected from the group consisting of thehalogenated, phosphorus, boron, silicon and antimony compounds, metalhydroxides, metal hydrates, metal oxides and mixtures thereof.
 22. Acomposition according to claim 21 wherein component (a) ispolypropylene, polyethylene or thermoplastic polyolefin (TPO).
 23. Acomposition according to claim 9 wherein component (a) is a paintablethermoplastic olefin (TPO).
 24. A composition according to claim 13wherein the coadditive stabilizer is a hindered phenolic antioxidantselected from the group consisting of neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate, octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5trimethyl-2,4,6-tris(3,5,-di-tert-butyl-4-hydroxybenzyl)benzene,1,2-bis(3,5-di-tert-butyl-hydroxyhydrocinnamoyl)hydrazine, calcium[bis(monoethyl 3,5-ditert-butylhydroxybenzyl)-phosphonate],1,3,5tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate; oris an organophosphorus stabilizer selected from the group consisting oftris(2,4-di-tert-butylphenyl) phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyl-tris-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], tetrakis(2,4-di-butylphenyl) 4,4′-biphenylenediphosphonite,tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite,2,2′-ethylidenebis(2,4-di-tert-butylphenyl)flurophosphite and2-butyl-2-ethylpropan-1,3-diyl 2,4,6-tri-tert-butylphenyl phosphite; oris 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-2H-benzofuran-2-one; or isN,N-dialkylhydroxylamine made by the direct oxidation ofN,N-di(hydrogenated tallow)amine; or is a hindered amine selected fromthe group consisting of bis(2,2,6,6-tetra-methylpiperidin-4-yl)sebacate, the polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, N, N′, N″,N″′-tetrakis[4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylenebis(amino-2,2,6,6tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, the polycondensation product of4,4′-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and2,4-dichloromorpholino-s-triazine, 2,2,6,6-tetramethylpiperidin-4-yloctadecanoate,3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-pyrrolidin-2,5-dione,1,3,5tris{N-cyclo-hexyl-N-[2-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)ethyl]amino}-s-triazine,poly[methyl 3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl]siloxane, thepolycondensation product of2,4-dichloro-6-(2,2,6,8tetramethylpiperidin-4-yl)butylamino)-s-triazine,2,2′ethylene-bis{[2,4-(2,2,6,6-tetramethylpiperidin-4-yl)butylamino-s-triazin-6-yl]aminotmethyleneamino},oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(2,2,6,6-tetra-methylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butyl-amino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N″′-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperdin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediimino-dipropylamine;or is another N-hydrocarbyloxy substituted hindered amines selected fromthe group consisting ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate, N,N′,N″-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperdin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineand N,N′,N″,N″′-tetrakis{2,4-bis[N-(1-cyclohexyloy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine;or is a UV absorber selected from the group consisting of2-(2-hydroxy-3,5di-α-cumylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone,2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxyoctyloxyphenyl)-s-triazine,oligomer ofN-{2-[(1-propoxy-2,2,6,6-tetramethyl-piperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, the condensationproduct of 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,6-hexanediamine; ormixtures thereof.
 25. A composition according to claim 24 wherein thecoadditive stabilizer is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate,tris(2,4-di-tert-butyl-phenyl) phosphite, N,N-dialkylhydroxylamine madeby the direct oxidation of N,N-di(hydrogenated tallow)amine, N, N′,N″,N″′-tetrakis[4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)amino-s-triazin-2-yl]-1,10diamino-4,7-diazadecane,the polycondensation product of4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-tert-octylamino-s-triazine, the polycondensation productof 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and2,4-dichloro-6-morpholino-s-triazine, the polycondensation product of4,4′-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and2,4-dichloromorpholino-s-triazine, oligomer ofN-{[2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}-N,N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,N,N′,N″-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,N,N′,N″′-tris{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamineandN,N′,N″,N′″-tetrakis{2,4-bis[N-(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazin-6-yl}-3,3′-ethylenediiminodipropylamine,oligomer ofN-{2-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazin-4-yl}N,N′-bis(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)-1,6-hexanediamineterminated with 2,4-bis(dibutylamino)-s-triazin-6-yl, or thecondensation product of 2-morpholino-4,6-dichloro-s-triazine withN,N′-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,6-hexanediamine.
 26. Acomposition according o claim 24 which additionally contains2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-d-tert-butyl-4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazolenornixtures-thereof.
 27. A composition according to claim 13wherein the coadditive stabilizer is a UV absorber selected from thegroup consisting of (a)5-trifluoromethyl-2-(2-hydroxy-3-a-cumyl-5-tert-octylphenyl)-2H-benzotriazole;(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;(c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;(d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];(e)methylene-2-[4-tert-octyl-6-(2H-benzotdazol-2-yl)phenol]2′-[4-tert-octyl-6-(5trifluoro-methyl-2H-benzotriazol-2-yl)phenol];(f)3-(5-trifluoromethyl-2H-benzotriazol-2-yi)-5-tert-butyl-4-hydroxyhydrocinnamicacid; (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;(h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;(i)5-tdfluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;(j)5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;(k)5-trifluoromethyl-2-[2-hydroxy-5(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;(l)5-trifluoromethyl-2-[2-hydroxy-5(3-acrylylaminopropyl)phenyl]-2H-benzotiazole;(m)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzo-triazole;(n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;(o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;(p)5tdfluoromethy-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzo-triazole;(q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)pheny]-2H-benzo-triazole;(r)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;(s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;(t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;(u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5(3-hydroxypropyl)phenyl)-2H-benzo-triazole;(v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5(2-hydroxyethyl)phenyl]-2H-benzo-triazole;(w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;(y) 5fluoro-2-(2-hydroxy-3,5di-α-cumylphenyl)-2H-benzotriazole; (z)5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;(aa)5butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;(bb)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;and (cc)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.28. A composition according to claim 9 which is a stabilized stovinglacquer wherein component (a) is an acid catalyzed resin based on hotcrosslinkable, acrylic, acrylic melamine, polyester, polyurethane,polyamide or alkyd resin.
 29. A composition according to claim 28 whichadditionally contains a UV absorber.
 30. A composition according toclaim 28 which is an enamel of high solids content for industrialfinishes.
 31. A composition according to claim 28 which is a finishingenamel for automobiles.
 32. A composition according to claim 9 which isa stabilized ambient curable composition wherein component (a) is aresin selected from the group consisting of unmodified or modified alkydresin, acrylic resin, acrylic alkyd resin, polyester resin orcrosslinkable epoxide resin.
 33. A composition according to claim 32wherein the resin is selected from the group consisting of unmodifiedalkyl, acrylic, acrylic alkyd or polyester resins; said resins modifiedwith silicon, isocyanates, isocyanurates, ketimines or oxazolidines;crosslinked epoxy resins; and epoxy-crosslinked acrylic and polyesterresins.
 34. A composition according to claim 32 which is an enamel ofhigh solids content for industrial finishes.
 35. A composition accordingto claim 32 which is a finishing enamel for automobiles.
 36. Acomposition according to claim 9 which is a curable electrocoatcomposition wherein component (a) is an amino-group containing resinhaving functional groups that are reactive with an isocyanate and anaromatic polyisocyanate crosslinking agent.
 37. A composition accordingto claim 9 which is a non-gelling liquid coating composition whereincomponent (a) comprises (A) at least one acrylic monomer, (B) silica and(C) at least one initiator for ultraviolet radication-induced curing ofsaid composition.
 38. A composition according to claim 37 which containsa silyl acrylate, a polyfunctional acrylate, silica and aphotoinitiator.